Systems and methods of producing a crude product

ABSTRACT

Contact of a crude feed with one or more catalysts containing a transition metal sulfide produces a total product that includes a crude product. The crude feed has a residue content of at least 0.2 grams of residue per gram of crude feed. The crude product is a liquid mixture at 25° C. and 0.101 MPa. One or more properties of the crude product may be changed by at least 10% relative to the respective properties of the crude feed. In some embodiments, gas is produced during contact with one or more catalysts and the crude feed.

PRIORITY CLAIM

This application claims priority to U.S. patent application Ser. No.11/014,297, which in turn claims priority to U.S. Provisional PatentApplication No. 60/531,506 entitled “METHODS OF PREPARING IMPROVED CRUDEFEED” filed on Dec. 19, 2003, and to U.S. Provisional Patent ApplicationNo. 60/618,814 entitled “SYSTEMS AND METHODS OF PRODUCING A CRUDEPRODUCT” filed on Oct. 14, 2004.

FIELD OF INVENTION

The present invention generally relates to systems and methods fortreating crude feed, and to compositions that are produced, for example,using such systems and methods. More particularly, embodiments describedherein relate to systems and methods for conversion of a crude feed thathas a residue content of at least 0.2 grams of residue per gram of crudefeed to a crude product that is (a) a liquid mixture at 25° C. and 0.101MPa, and (b) has one or more properties that are improved in comparisonto the same properties of the crude feed.

DESCRIPTION OF RELATED ART

Crudes that have one or more unsuitable properties that do not allow thecrudes to be economically transported, or processed using conventionalfacilities, are commonly referred to as “disadvantaged crudes”.

Disadvantaged crudes often contain relatively high levels of residue.Such crudes tend to be difficult and expensive to transport and/orprocess using conventional facilities. High residue crudes may betreated at high temperatures to convert the crude to coke.Alternatively, high residue crudes are typically treated with water athigh temperatures to produce less viscous crudes and/or crude mixtures.During processing, water removal from the less viscous crudes and/orcrude mixtures may be difficult using conventional means.

Disadvantaged crudes may include hydrogen deficient hydrocarbons. Whenprocessing of hydrogen deficient hydrocarbons, consistent quantities ofhydrogen generally need to be added, particularly if unsaturatedfragments resulting from cracking processes are produced. Hydrogenationduring processing, which typically involves the use of an activehydrogenation catalyst, may be needed to inhibit unsaturated fragmentsfrom forming coke. Hydrogen is costly to produce and/or costly totransport to treatment facilities.

Coke may form and/or deposit on catalyst surfaces at a rapid rate duringprocessing of disadvantaged crudes. It may be costly to regenerate thecatalytic activity of a catalyst contaminated by coke. High temperaturesused during regeneration may also diminish the activity of the catalystand/or cause the catalyst to deteriorate.

Disadvantaged crudes may include acidic components that contribute tothe total acid number (“TAN”) of the crude feed. Disadvantaged crudeswith a relatively high TAN may contribute to corrosion of metalcomponents during transporting and/or processing of the disadvantagedcrudes. Removal of acidic components from disadvantaged crudes mayinvolve chemically neutralizing acidic components with various bases.Alternately, corrosion-resistant metals may be used in transportationequipment and/or processing equipment. The use of corrosion-resistantmetal often involves significant expense, and thus, the use ofcorrosion-resistant metal in existing equipment may not be desirable.Another method to inhibit corrosion may involve addition of corrosioninhibitors to disadvantaged crudes before transporting and/or processingof the disadvantaged crudes. The use of corrosion inhibitors maynegatively affect equipment used to process the crudes and/or thequality of products produced from the crudes.

Disadvantaged crudes may contain relatively high amounts of metalcontaminants, for example, nickel, vanadium, and/or iron. Duringprocessing of such crudes, metal contaminants, and/or compounds of metalcontaminants, may deposit on a surface of the catalyst or the voidvolume of the catalyst. Such deposits may cause a decline in theactivity of the catalyst.

Disadvantaged crudes often include organically bound heteroatoms (forexample, sulfur, oxygen, and nitrogen). Organically bound heteroatomsmay, in some situations, have an adverse effect on catalysts. Alkalimetal salts and/or alkaline-earth metal salts have been used inprocesses for desulfurization of residue. These processes tend to resultin poor desulfurization efficiency, production of oil insoluble sludge,poor demetallization efficiency, formation of substantially inseparablesalt-oil mixtures, utilization of large quantities of hydrogen gas,and/or relatively high hydrogen pressures.

Some processes for improving the quality of crude include adding adiluent to disadvantaged crudes to lower the weight percent ofcomponents contributing to the disadvantaged properties. Adding diluent,however, generally increases costs of treating disadvantaged crudes dueto the costs of diluent and/or increased costs to handle thedisadvantaged crudes. Addition of diluent to a disadvantaged crude may,in some situations, decrease stability of such crude.

U.S. Pat. No. 3,136,714 to Gibson et al.; U.S. Pat. No. 3,558,747 toGleim et al.; U.S. Pat. No. 3,847,797 to Pasternak et al.; U.S. Pat. No.3,948,759 to King et al.; U.S. Pat. No. 3,957,620 to Fukui et al.; U.S.Pat. No. 3,960,706 to McCollum et al.; U.S. Pat. No. 3,960,708 toMcCollum et al.; U.S. Pat. No. 4,119,528 to Baird, Jr. et al.; U.S. Pat.No. 4,127,470 to Baird, Jr. et al.; U.S. Pat. No. 4,224,140 to Fujimoriet al.; U.S. Pat. No. 4,437,980 to Heredy et al.; U.S. Pat. No.4,591,426 to Krasuk et al.; U.S. Pat. No. 4,665,261 to Mazurek; U.S.Pat. No. 5,064,523 to Kretschmar et al.; U.S. Pat. No. 5,166,118 toKretschmar et al.; U.S. Pat. No. 5,288,681 to Gatsis; U.S. Pat. No.6,547,957 to Sudhakar et al.; and U.S. Patent Application PublicationNos. 20030000867 to Reynolds and 20030149317 to Rendina, all of whichare incorporated herein by reference, describe various processes andsystems used to treat crudes. The process, systems, and catalystsdescribed in these patents, however, have limited applicability becauseof many of the technical problems set forth above.

In sum, disadvantaged crudes generally have undesirable properties (forexample, relatively high residue, a tendency to corrode equipment,and/or a tendency to consume relatively large amounts of hydrogen duringtreatment). Other undesirable properties include relatively high amountsof undesirable components (for example, relatively high TAN, organicallybound heteroatoms, and/or metal contaminants). Such properties tend tocause problems in conventional transportation and/or treatmentfacilities, including increased corrosion, decreased catalyst life,process plugging, and/or increased usage of hydrogen during treatment.Thus, there is a significant economic and technical need for improvedsystems, methods, and/or catalysts for conversion of disadvantagedcrudes into crude products with properties that are more desirable.

SUMMARY OF THE INVENTION

Inventions described herein generally relate to systems and methods forcontacting a crude feed with one or more catalysts to produce a totalproduct comprising a crude product and, in some embodiments,non-condensable gas. Inventions described herein also generally relateto compositions that have novel combinations of components therein. Suchcompositions can be obtained by using the systems and methods describedherein.

In certain embodiments, the invention provides a method of preparing acrude product, comprising contacting a crude feed with a hydrogen sourcein the presence of one or more catalysts comprising a transition metalsulfide catalyst to produce a total product that includes the crudeproduct, wherein the crude product is a liquid mixture at 25° C. and0.101 MPa, and the transition metal sulfide catalyst comprisesK₃Fe₁₀S₁₄.

In certain embodiments, the invention provides a method of producing acrude product, comprising: contacting a crude feed with a hydrogensource in the presence of one or more catalysts to produce a totalproduct that includes the crude product, wherein the crude product is aliquid mixture at 25° C. and 0.101 MPa, at least one of the catalystscomprising one or more transition metal sulfides, and the crude feedhaving a residue content of at least 0.2 grams of residue per gram ofcrude feed, as determined by ASTM Method D5307; and controllingcontacting conditions such that the crude product has at most 0.05 gramsof coke per gram of crude product, the crude product has at least 0.001grams of naphtha per gram of crude product, and the naphtha has anoctane number of at least 70.

In some embodiments, the invention provides a method of preparing acrude product, comprising: contacting a crude feed with a hydrogensource in the presence of one or more catalysts to produce a totalproduct that includes the crude product, wherein the crude product is aliquid mixture at 25° C. and 0.101 MPa, at least one of the catalystscomprising one or more transition metal sulfides, and the crude feedhaving a residue content of at least 0.2 grams of residue per gram ofcrude feed, as determined by ASTM Method D5307; and controllingcontacting conditions such that the crude product comprises kerosene,the kerosene having at least 0.2 grams of aromatics per gram ofkerosene, as determined by ASTM Method D5186, the kerosene having afreezing point at a temperature of at most −30° C., as determined byASTM Method D2386, and the crude product having at most 0.05 grams ofcoke per gram of crude product.

In certain embodiments, the invention provides a method of producing acrude product, comprising: contacting a crude feed with a hydrogensource in the presence of one or more catalysts to produce a totalproduct that includes the crude product, wherein the crude product is aliquid mixture at 25° C. and 0.101 MPa, at least one of the catalystscomprising one or more transition metal sulfides, and the crude feedhaving a residue content of at least 0.2 grams of residue per gram ofcrude feed; and controlling contacting conditions such that the crudeproduct has at most 0.05 grams of coke per gram of crude product with aweight ratio of atomic hydrogen to atomic carbon (H/C) in the crudeproduct of at most 1.75, as determined by ASTM Method D6730.

In some embodiments, the invention provides a method of producing acrude product, comprising: contacting a crude feed with a hydrogensource in the presence of one or more catalysts to produce a totalproduct that includes the crude product, wherein the crude product is aliquid mixture at 25° C. and 0.101 MPa, at least one of the catalystscomprising one or more transition metal sulfides, and the crude feedhaving a residue content of at least 0.2 grams of residue per gram ofcrude feed, as determined by ASTM Method D5307, and a weight ratio ofatomic hydrogen to atomic carbon (H/C) in the crude feed is at least1.5; and controlling contacting conditions such that the crude producthas an atomic H/C ratio of about 80-120% of the atomic H/C ratio of thecrude feed, the crude product having a residue content of at most 30% ofthe residue content of the crude feed, as determined by ASTM MethodD5307, the crude product having at least 0.001 grams of naphtha per gramof crude product, and the naphtha having an octane number of at least70.

In certain embodiments, the invention provides a method of producing acrude product, comprising: contacting a crude feed with a hydrogensource in the presence of one or more catalysts, to produce a totalproduct that includes the crude product, wherein the crude product is aliquid mixture at 25° C. and 0.101 MPa, at least one of the catalystscomprising one or more transition metal sulfides, and the crude feed hasa residue content of at least 0.2 grams of residue per gram of crudefeed, as determined by ASTM Method D5307; and controlling contactingconditions such that the crude product has, per gram of crude product:at least 0.001 grams of naphtha, the naphtha having an octane number ofat least 70; at least 0.001 grams of kerosene, the kerosene comprisingaromatics, the kerosene having at least 0.2 grams of aromatics per gramof kerosene, as determined by ASTM Method D5186, and the kerosene havinga freezing point at a temperature of at most −30° C., as determined byASTM Method D2386; at least 0.001 grams of vacuum gas oil (VGO), the VGOhaving at least 0.3 grams of aromatics per gram of VGO, as determined byIP Method 368/90; and at most 0.05 grams of residue, as determined byASTM Method D5307.

In some embodiments, the invention provides a method of producing acrude product, comprising: contacting a crude feed with a hydrogensource in the presence of one or more catalysts comprising a transitionmetal sulfide catalyst to produce a total product that includes thecrude product, wherein the crude product is a liquid mixture at 25° C.and 0.101 MPa, the transition metal sulfide catalyst having a total ofat least 0.4 grams of one or more transition metal sulfides per gram oftotal transition metal sulfide catalyst, the crude feed having a residuecontent of at least 0.2 grams of residue per gram of crude feed, asdetermined by ASTM Method D5307; and controlling contacting conditionssuch that the crude product has at most 0.05 grams of coke per gram ofcrude product, and the crude product has a residue content of at most30% of the residue content of the crude feed, as determined by ASTMMethod D5307.

In certain embodiments, the invention provides a method of producing acrude product, comprising: contacting a crude feed with a hydrogensource in the presence of one or more catalysts comprising a transitionmetal sulfide catalyst to produce a total product that includes thecrude product, wherein the crude product is a liquid mixture at 25° C.and 0.101 MPa, the transition metal sulfide catalyst having a total ofleast 0.4 grams of one or more transition metal sulfides per gram oftransition metal sulfide catalyst, the crude feed having a nitrogencontent of at least 0.001 grams of nitrogen per gram of crude feed, andthe crude feed having a residue content of at least 0.2 grams of residueper gram of crude feed; and controlling contacting conditions such thatthe crude product has a nitrogen content of at most 90% of the nitrogencontent of the crude feed, and the crude product has a residue contentof at most 30% of the residue content of the crude feed, whereinnitrogen content is as determined by ASTM Method D5762 and residuecontent is as determined by ASTM Method D5307.

In some embodiments, the invention provides a method of producing acrude product, comprising: contacting a crude feed with a hydrogensource in the presence of one or more catalysts comprising a transitionmetal sulfide catalyst to produce a total product that includes thecrude product, wherein the crude product is a liquid mixture at 25° C.and 0.101 MPa, the transition metal sulfide catalyst has a total ofleast 0.4 grams of one or more transition metal sulfides per gram oftotal transition metal sulfide catalyst, the crude feed has a totalNi/V/Fe content of at least 0.0001 grams of Ni/V/Fe per gram of crudefeed, and the crude feed has a residue content of at least 0.2 grams ofresidue per gram of crude feed; and controlling contacting conditionssuch that the crude product has at most 0.05 grams of coke per gram ofcrude product, the crude product has a total Ni/V/Fe content of at most90% of the Ni/V/Fe content of the crude feed, the crude product has aresidue content of at most 30% of the residue content of the crude feed,and wherein Ni/V/Fe content is as determined by ASTM Method D5863, andresidue content is as determined by ASTM Method D5307.

In some embodiments, the invention provides a method of producing acrude product, comprising: contacting a crude feed with a hydrogensource in the presence of one or more catalysts comprising a transitionmetal sulfide catalyst to produce a total product that includes thecrude product, wherein the crude product is a liquid mixture at 25° C.and 0.101 MPa, the transition metal sulfide catalyst having a total ofat least 0.4 grams of one or more transition metal sulfides per gram oftotal transition metal sulfide catalyst, the crude feed having a sulfurcontent of at least 0.001 grams of sulfur per gram of crude feed, andthe crude feed having a residue content at least 0.2 grams of residueper gram of crude feed; and controlling contacting conditions such thatthe crude product has a sulfur content of at most 70% of the sulfurcontent of the crude feed, and the crude product has a residue contentof at most 30% of the residue content of the crude feed, wherein sulfurcontent is as determined by ASTM Method D4294 and residue content is asdetermined by ASTM Method D5307.

In certain embodiments, the invention provides a method of producing atransition metal sulfide catalyst composition, comprising: mixing atransition metal oxide and a metal salt to form a transition metaloxide/metal salt mixture; reacting the transition metal oxide/metal saltmixture with hydrogen to form an intermediate; and reacting theintermediate with sulfur in the presence of one or more hydrocarbons toproduce the transition metal sulfide catalyst.

In some embodiments, the invention provides a method of producing acrude product, comprising: contacting a crude feed with a hydrogensource in the presence of one or more catalysts comprising a transitionmetal sulfide catalyst to produce a total product that includes thecrude product, wherein the crude product is a liquid mixture at 25° C.and 0.101 MPa, the transition metal sulfide catalyst comprises atransition metal sulfide, the crude feed having a residue content of atleast 0.2 grams of residue per gram of crude feed, as determined by ASTMMethod D5307; controlling contact conditions such that the crude producthas a residue content of at most 30% of the residue content of the crudefeed; and wherein the transition metal sulfide catalyst is obtainableby: mixing a transition metal oxide and a metal salt to form atransition metal oxide/metal salt mixture; reacting the transition metaloxide/metal salt mixture with hydrogen to form an intermediate; andreacting the intermediate with sulfur in the presence of one or morehydrocarbons to produce the transition metal sulfide catalyst.

In certain embodiments, the invention provides a method of producing acrude product, comprising: contacting a crude feed with a hydrogensource in the presence of one or more catalysts to produce a totalproduct that includes the crude product, wherein the crude product is aliquid mixture at 25° C. and 0.101 MPa, and the crude feed having atleast 0.2 grams of residue per gram of crude feed, as determined by ASTMMethod D5307; producing at least a portion of the total product as avapor; condensing at least a portion of the vapor at 25° C. and 0.101MPa; and forming the crude product, wherein the crude product has, pergram of crude product: at least 0.001 grams of naphtha, the naphthahaving an octane number of at least 70; at least 0.001 grams of vacuumgas oil (VGO), the VGO having at least 0.3 grams of aromatics per gramof VGO, as determined by IP Method 368/90; and at most 0.05 grams ofresidue, as determined by ASTM Method D5307.

In some embodiments, the invention provides a method of producing acrude product, comprising: contacting a crude feed with a hydrogensource in the presence of an inorganic salt catalyst to produce a totalproduct that includes the crude product, wherein the crude feed has aresidue content of at least 0.2 grams of residue per gram of crude feed,as determined by ASTM Method D5307, the crude product is a liquidmixture at 25° C. and 0.101 MPa, and the crude product has, per gram ofcrude product: at least 0.001 grams of naphtha, the naphtha having atleast 0.001 grams of monocyclic ring aromatics per gram of naphtha, asdetermined by ASTM Method D6730; at least 0.001 grams of distillate; andat most 0.05 grams of residue, as determined by ASTM Method D5307.

In certain embodiments, the invention provides a method of producing acrude product, comprising: contacting a crude feed with a hydrogensource in the presence of an inorganic salt catalyst to produce a totalproduct that includes the crude product, wherein the crude feed has aresidue content of at least 0.2 grams of residue per gram of crude feed,as determined by ASTM Method D5307, the crude product is a liquidmixture at 25° C. and 0.101 MPa, and the crude product has, per gram ofcrude product: at least 0.001 grams of diesel, and the diesel has atleast 0.3 grams of aromatics per gram of diesel, as determined by IPMethod 368/90; at least 0.001 grams of vacuum gas oil (VGO), and the VGOhas at least 0.3 grams of aromatics per gram of VGO, as determined by IPMethod 368/90; and at most 0.05 grams of residue, as determined by ASTMMethod D5307.

In some embodiments, the invention provides a method of producing acrude product, comprising: contacting a crude feed with a hydrogensource in the presence of an inorganic salt catalyst to produce a totalproduct that includes the crude product, wherein the crude product is aliquid mixture at 25° C. and 0.101 MPa, the crude feed has a residuecontent of at least 0.2 grams of residue per gram of crude feed, asdetermined by ASTM Method D5307, and the crude feed has a monocyclicring aromatics content of at most 0.1 grams of monocyclic ring aromaticsper gram of crude feed; and controlling contacting conditions such thatduring the contacting at most 0.2 grams of hydrocarbons that are notcondensable at 25° C. and 0.101 MPa are formed per gram of crude feed,as determined by mass balance, and such that the crude product has amonocyclic ring aromatics content of at least 5% greater than amonocyclic ring aromatics content of the crude feed, wherein monocyclicring aromatics content is as determined by ASTM Method D6730.

In certain embodiments, the invention provides a method of producing acrude product, comprising: contacting a crude feed with a hydrogensource in the presence of an inorganic salt catalyst to a produce atotal product that includes the crude product, wherein the crude productis a liquid mixture at 25° C. and 0.101 MPa, the crude feed has aresidue content of at least 0.2 grams of residue per gram of crude feed,as determined by ASTM Method D5307, and the crude feed has an olefinscontent, expressed in grams of olefins per gram of crude feed; andcontrolling contacting conditions such that the crude product has anolefins content of at least 5% greater than the olefins content of thecrude feed, wherein olefin content is as determined by ASTM MethodD6730.

In some embodiments, the invention provides a method of producing acrude product, comprising: contacting a crude feed with a hydrogensource in the presence of an inorganic salt catalyst to produce a totalproduct that includes the crude product, wherein the crude product is aliquid mixture at 25° C. and 0.101 MPa, the crude feed having a residuecontent of at least 0.2 grams of residue per gram of crude feed, and theinorganic salt catalyst exhibits an emitted gas inflection of an emittedgas in a temperature range between about 50° C. and about 500° C., asdetermined by Temporal Analysis of Products (TAP); and controllingcontacting conditions such that the crude product has a residue content,expressed in grams of residue per gram of crude product, of at most 30%of the residue content of the crude feed, wherein residue content is asdetermined by ASTM Method D5307.

In certain embodiments, the invention provides a method of producing acrude product, comprising: contacting a crude feed with a hydrogensource in the presence of an inorganic salt catalyst to produce a totalproduct that includes the crude product, wherein the crude product is aliquid mixture at 25° C. and 0.101 MPa, the crude feed has a residuecontent of at least 0.2 grams of residue per gram of crude feed, theinorganic salt catalyst comprises at least two inorganic metal salts,and the inorganic salt catalyst exhibits an emitted gas inflection of anemitted gas in a temperature range, as determined by Temporal Analysisof Products (TAP), wherein the emitted gas inflection temperature rangeis between (a) a DSC temperature of at least one of the two inorganicmetal salts and (b) a DSC temperature of the inorganic salt catalyst;and controlling contacting conditions such that the crude product has aresidue content, expressed in grams of residue per gram of crudeproduct, of at most 30% of the residue content of the crude feed,wherein residue content is as determined by ASTM Method D5307.

In some embodiments, the invention provides a method of producing acrude product, comprising: contacting a crude feed with a hydrogensource in the presence of an inorganic salt catalyst to produce a totalproduct that includes the crude product, wherein the crude product is aliquid mixture at 25° C. and 0.101 MPa, the crude feed has a residuecontent of at least 0.2 grams of residue per gram of crude feed, asdetermined by ASTM Method D5307, and the inorganic salt catalystexhibits an emitted gas inflection of an emitted gas in a temperaturerange between about 50° C. and about 500° C., as determined by TemporalAnalysis of Products (TAP); and producing the crude product such that avolume of the crude product produced is at least 5% greater than thevolume of the crude feed, when the volumes are measured at 25° C. and0.101 MPa.

In certain embodiments, the invention provides a method of producing acrude product, comprising: contacting a crude feed with a hydrogensource in the presence of an inorganic salt catalyst to produce a totalproduct that includes the crude product, wherein the crude product is aliquid mixture at 25° C. and 0.101 MPa, the crude feed has a residuecontent of at least 0.2 grams of residue per gram of crude feed, and theinorganic salt catalyst exhibits an emitted gas inflection of an emittedgas in a temperature range between about 50° C. and about 500° C., asdetermined by Temporal Analysis of Products (TAP); and controllingcontacting conditions such that during the contacting at most 0.2 gramsof hydrocarbons that are not condensable at 25° C. and 0.101 MPa areformed per gram of crude feed, as determined by mass balance.

In some embodiments, the invention provides a method of producing acrude product, comprising: contacting a crude feed with a hydrogensource in the presence of an inorganic salt catalyst to produce a totalproduct that includes the crude product, wherein the crude product is aliquid mixture at 25° C. and 0.101 MPa, the crude feed having a residuecontent of at least 0.2 grams of residue per gram of crude feed, and theinorganic salt catalyst has a heat transition in a temperature rangebetween about 200° C. and about 500° C., as determined by differentialscanning calorimetry (DSC), at a rate of about 10° C. per minute; andcontrolling contacting conditions such that the crude product has aresidue content, expressed in grams of residue per gram of crudeproduct, of at most 30% of the residue content of the crude feed,wherein residue content is as determined by ASTM Method D5307.

In certain embodiments, the invention provides a method of producing acrude product, comprising: contacting a crude feed with a hydrogensource in the presence of an inorganic salt catalyst to produce a totalproduct that includes the crude product, wherein the crude product is aliquid mixture at 25° C. and 0.101 MPa, the crude feed having a residuecontent of at least 0.2 grams of residue per gram of crude feed, and theinorganic salt catalyst has ionic conductivity that is at least theionic conductivity of at least one of the inorganic salts of theinorganic salt catalyst at a temperature in a range from about 300° C.and about 500° C.; and controlling contacting conditions such that thecrude product has a residue content, expressed in grams of residue pergram of crude product, of at most 30% of the residue content of thecrude feed, wherein residue content is as determined by ASTM MethodD5307.

In certain embodiments, the invention provides a method of producing acrude product, comprising: contacting a crude feed with a hydrogensource in the presence of an inorganic salt catalyst to produce a totalproduct that includes the crude product, wherein the crude product is aliquid mixture at 25° C. and 0.101 MPa, the crude feed has a residuecontent of at least 0.2 grams of residue per gram of crude feed, theinorganic salt catalyst comprises alkali metal salts, wherein at leastone of the alkali metal salts is an alkali metal carbonate, and thealkali metals have an atomic number of at least 11, and at least oneatomic ratio of an alkali metal having an atomic number of at least 11to an alkali metal having an atomic number greater than 11 is in a rangefrom about 0.1 to about 10; and controlling contacting conditions suchthat the crude product has a residue content of at most 30% of theresidue content of the crude feed, wherein residue content is asdetermined by ASTM Method D5307.

In some embodiments, the invention provides a method of producing acrude product, comprising: contacting a crude feed with a hydrogensource in the presence of an inorganic salt catalyst to produce a totalproduct, wherein the crude feed has a residue content of at least 0.2grams of residue per gram of crude feed, the inorganic salt catalystcomprises alkali metal salts, wherein at least one of the alkali metalsalts is an alkali metal hydroxide, and the alkali metals have an atomicnumber of at least 11, and at least one atomic ratio of an alkali metalhaving an atomic number of at least 11 to an alkali metal having anatomic number greater than 11 is in a range from about 0.1 to about 10;producing at least a portion of the total product as a vapor; condensingat least a portion of the vapor at 25° C. and 0.101 MPa; and forming thecrude product, wherein the crude product has a residue content of atmost 30% of the residue content of the crude feed.

In certain embodiments, the invention provides a method of producing acrude product, comprising: contacting a crude feed with a hydrogensource in the presence of an inorganic salt catalyst to produce a totalproduct, wherein the crude feed has a residue content of at least 0.2grams of residue per gram of crude feed, the inorganic salt catalystcomprises alkali metal salts, wherein at least one of the alkali metalsalts is an alkali metal hydride, and the alkali metals have an atomicnumber of at least 11, and at least one atomic ratio of an alkali metalhaving an atomic number of at least 11 to an alkali metal having anatomic number greater than 11 is in a range from about 0.1 to about 10;producing at least a portion of the total product as a vapor; condensingat least a portion of the vapor at 25° C. and 0.101 MPa; and forming thecrude product, wherein the crude product has a residue content of atmost 30% of the residue content of the crude feed.

In some embodiments, the invention provides a method of producing acrude product, comprising: contacting a crude feed with a hydrogensource in the presence of an inorganic salt catalyst to produce a totalproduct that includes the crude product, wherein the crude product is aliquid mixture at 25° C. and 0.101 MPa, the crude feed has a residuecontent of at least 0.2 grams of residue per gram of crude feed, theinorganic salt catalyst comprises one or more alkali metal salts, one ormore alkaline-earth metal salts, or mixtures thereof, wherein one of thealkali metal salts is an alkali metal carbonate, wherein the alkalimetals have an atomic number of at least 11; and controlling contactingconditions such that the crude product has a residue content of at most30% of the residue content of the crude feed, wherein residue content isas determined by ASTM Method D5307.

In certain embodiments, the invention provides a method of producing acrude product, comprising: contacting a crude feed with a hydrogensource in the presence of an inorganic salt catalyst to produce a totalproduct that includes the crude product, wherein the crude product is aliquid mixture at 25° C. and 0.101 MPa, the crude feed has a residuecontent of at least 0.2 grams of residue per gram of crude feed, theinorganic salt catalyst comprises one or more alkali metal hydroxides,one or more alkaline-earth metal salts, or mixtures thereof, wherein thealkali metals have an atomic number of at least 11; and controllingcontacting conditions such that the crude product has a residue contentof at most 30% of the residue content of the crude feed, wherein residuecontent is as determined by ASTM Method D5307.

In some embodiments, the invention provides a method of producing acrude product, comprising: contacting a crude feed with a hydrogensource in the presence of an inorganic salt catalyst to produce a totalproduct that includes the crude product, wherein the crude product is aliquid mixture at 25° C. and 0.101 MPa, the crude feed has a residuecontent of at least 0.2 grams of residue per gram of crude feed, theinorganic salt catalyst comprises one or more alkali metal hydrides, oneor more alkaline-earth salts, or mixtures thereof, and wherein thealkali metals have an atomic number of at least 11; and controllingcontacting conditions such that the crude product has a residue content,expressed in grams of residue per gram of crude product, of at most 30%of the residue content of the crude feed, wherein residue content is asdetermined by ASTM Method D5307.

In certain embodiments, the invention provides a method of producinghydrogen gas, comprising: contacting a crude feed with one or morehydrocarbons in the presence of an inorganic salt catalyst and water,the hydrocarbons have carbon numbers in a range from 1 to 6, the crudefeed has a residue content of at least 0.2 grams of residue per gram ofcrude feed, and the inorganic salt catalyst exhibits an emitted gasinflection of an emitted gas in a temperature range between about 50° C.and about 500° C., as determined by Temporal Analysis of Products (TAP);and producing hydrogen gas.

In some embodiments, the invention provides a method of producing acrude product, comprising: contacting a first crude feed with aninorganic salt catalyst in the presence of steam to generate a gasstream, the gas stream comprising hydrogen, wherein the first crude feedhas a residue content of at least 0.2 grams of residue per gram of firstcrude feed, as determined using ASTM Method D5307, and the inorganicsalt catalyst exhibits an emitted gas inflection of an emitted gas in atemperature range between about 50° C. and about 500° C., as determinedby Temporal Analysis of Products (TAP); contacting a second crude feedwith a second catalyst in the presence of at least a portion of thegenerated gas stream to produce a total product that includes the crudeproduct, wherein the crude product is a liquid mixture at 25° C. and0.101 MPa; and controlling contacting conditions such that one or moreproperties of the crude product change by at least 10% relative to therespective one or more properties of the second crude feed.

In certain embodiments, the invention provides a method of generating agas stream, comprising: contacting a crude feed with an inorganic saltcatalyst in the presence of steam, wherein the crude feed has a residuecontent of at least 0.2 grams of residue per gram of crude feed, asdetermined by ASTM Method 5307; and generating a gas stream, the gasstream comprising hydrogen, carbon monoxide, and carbon dioxide, andwherein a molar ratio of the carbon monoxide to the carbon dioxide is atleast 0.3.

In some embodiments, the invention provides a method of producing acrude product comprising: conditioning an inorganic salt catalyst;contacting a crude feed with a hydrogen source in the presence of theconditioned inorganic salt catalyst to produce a total product thatincludes the crude product, wherein the crude product is a liquidmixture at 25° C. and 0.101 MPa, the crude feed having a residue contentof at least 0.2 grams of residue per gram of crude feed; and controllingcontacting conditions such that the crude product has a residue content,expressed in grams of residue per gram of crude product, of at most 30%of the residue content of the crude feed, wherein residue content is asdetermined by ASTM Method D5307.

In certain embodiments, the invention provides a crude composition,comprising hydrocarbons that have a boiling range distribution betweenabout 30° C. and about 538° C. (1,000° F.) at 0.101 MPa, thehydrocarbons comprising iso-paraffins and n-paraffins with a weightratio of the iso-paraffins to n-paraffins of at most 1.4, as determinedby ASTM Method D6730.

In some embodiments, the invention provides a crude composition having,per gram of composition: at least 0.001 grams of hydrocarbons with aboiling range distribution of at most 204° C. (400° F.) at 0.101 MPa, atleast 0.001 grams of hydrocarbons with a boiling range distributionbetween about 204° C. and about 300° C. at 0.101 MPa, at least 0.001grams of hydrocarbons with a boiling range distribution between about300° C. and about 400° C. at 0.101 MPa, and at least 0.001 grams ofhydrocarbons with a boiling range distribution between about 400° C. andabout 538° C. (1,000° F.) at 0.101 MPa, and wherein the hydrocarbonsthat have a boiling range distribution of at most 204° C. compriseiso-paraffins and n-paraffins with a weight ratio of the iso-paraffinsto the n-paraffins of at most 1.4, as determined by ASTM Method D6730.

In certain embodiments, the invention provides a crude compositionhaving, per gram of composition: at least 0.001 grams of naphtha, thenaphtha having an octane number of at least 70, and the naphtha havingat most 0.15 grams of olefins per gram of naphtha, as determined by ASTMMethod D6730; at least 0.001 grams of kerosene, the kerosene having atleast 0.2 grams of aromatics per gram of kerosene, as determined by ASTMD5186, and the kerosene having a freezing point at a temperature of atmost −30° C., as determined by ASTM Method D2386; and at most 0.05 gramsof residue, as determined by ASTM Method D5307.

In some embodiments, the invention provides a crude composition having,per gram of composition: at most 0.15 grams of hydrocarbon gas that isnon-condensable at 25° C. and 0.101 MPa, the non-condensable hydrocarbongas having at most 0.3 grams of hydrocarbons with a carbon number from 1to 3 (C₁ to C₃), per gram of non-condensable hydrocarbon gas; at least0.001 grams of naphtha, the naphtha having an octane number of at least70; at least 0.001 grams of kerosene, the kerosene having a freezingpoint at a temperature of at most −30° C., as determined by ASTM MethodD2386, and the kerosene having at least 0.2 grams of aromatics per gramof kerosene, as determined by ASTM Method D5186; and at most 0.05 gramsof residue, as determined by ASTM Method D5307.

In certain embodiments, the invention provides a crude composition,having, per gram of composition: at most 0.05 grams of residue, asdetermined by ASTM Method D5307; at least 0.001 grams of hydrocarbonswith a boiling range distribution of at most 204° C. (400° F.) at 0.101MPa; at least 0.001 grams of hydrocarbons with a boiling rangedistribution between about 204° C. and about 300° C. at 0.101 MPa; atleast 0.001 grams of hydrocarbons with a boiling range distributionbetween about 300° C. and about 400° C. at 0.101 MPa; at least 0.001grams of hydrocarbons with a boiling range distribution between about400° C. and about 538° C. (1,000° F.) at 0.101 MPa; and wherein thehydrocarbons in a boiling range distribution between about 20° C. andabout 204° C. comprise olefins having terminal double bonds and olefinshaving internal double bonds with a molar ratio of olefins havingterminal double bonds to olefins having internal double bonds of atleast 0.4, as determined by ASTM Method D6730.

In some embodiments, the invention provides a crude composition, having,per gram of composition: at most 0.05 grams of residue, as determined byASTM Method D5307; and at least 0.001 grams of a mixture of hydrocarbonsthat have a boiling range distribution between about 20° C. and about538° C. (1,000° F.), as determined by ASTM Method D5307, and thehydrocarbon mixture has, per gram of hydrocarbon mixture: at least 0.001grams of paraffins, as determined by ASTM Method D6730; at least 0.001grams of olefins, as determined by ASTM Method D6730, and the olefinshave at least 0.001 grams of terminal olefins per gram of olefins, asdetermined by ASTM Method D6730; at least 0.001 grams of naphtha; atleast 0.001 grams of kerosene, the kerosene having at least 0.2 grams ofaromatics per gram of kerosene, as determined by ASTM Method D5186; atleast 0.001 grams of diesel, the diesel having at least 0.3 grams ofaromatics per gram of diesel, as determined by IP Method 368/90; and atleast 0.001 grams of vacuum gas oil (VGO), the VGO having at least 0.3grams of aromatics per gram of VGO, as determined by IP Method 368/90.

In certain embodiments, the invention provides a crude compositionhaving, per gram of composition: at most 0.05 grams of residue, asdetermined by ASTM Method D5307; at least 0.001 grams of hydrocarbonswith a boiling range distribution of at most 204° C. (400° F.) at 0.101MPa; at least 0.001 grams of hydrocarbons with a boiling rangedistribution between about 204° C. and about 300° C. at 0.101 MPa; atleast 0.001 grams of hydrocarbons with a boiling range distributionbetween about 300° C. and about 400° C. at 0.101 MPa; and at least 0.001grams of hydrocarbons with a boiling range distribution between about400° C. and about 538° C. (1,000° F.) at 0.101 MPa, as determined byASTM Method D2887; and wherein the hydrocarbons having a boiling rangedistribution of at most 204° C. have, per gram of hydrocarbons having aboiling range distribution of at most 204° C.: at least 0.001 grams ofolefins, as determined by ASTM Method D6730; and at least 0.001 grams ofparaffins, the paraffins comprising iso-paraffins and n-paraffins with aweight ratio of iso-paraffins to n-paraffins of at most 1.4, asdetermined by ASTM Method D6730.

In some embodiments, the invention provides a crude composition having,per gram of composition: at most 0.05 grams of residue, as determined byASTM Method D5307; and at least 0.001 grams of hydrocarbons with aboiling range distribution of at most 204° C. (400° F.) at 0.101 MPa; atleast 0.001 grams of hydrocarbons with a boiling range distributionbetween about 204° C. and about 300° C. at 0.101 MPa; at least 0.001grams of hydrocarbons with a boiling range distribution between about300° C. and about 400° C. at 0.101 MPa; and at least 0.001 grams ofhydrocarbons with a boiling range distribution between about 400° C. andabout 538° C. (1,000° F.) at 0.101 MPa, as determined by ASTM MethodD2887; and wherein the hydrocarbons having a boiling range distributionbetween about −10° C. and about 204° C. comprise compounds with a carbonnumber of 4 (C₄), the C₄ compounds having at least 0.001 grams ofbutadiene per gram of C₄ compounds.

In certain embodiments, the invention provides a crude compositionhaving, per gram of composition: at most 0.05 grams of residue; at least0.001 grams of hydrocarbons with a boiling range distribution of at most204° C. (400° F.) at 0.101 MPa, at least 0.001 grams of hydrocarbonswith a boiling range distribution between about 204° C. and about 300°C. at 0.101 MPa, at least 0.001 grams of hydrocarbons with a boilingrange distribution between about 300° C. and about 400° C. at 0.101 MPa,and at least 0.001 grams of hydrocarbons with a boiling rangedistribution between about 400° C. and about 538° C. at 0.101 MPa; andgreater than 0 grams, but less than 0.01 grams of one or more catalyst,wherein the catalyst has at least one or more alkali metals.

In some embodiments, the invention also provides, in combination withone or more of the above embodiments, a crude feed that: (a) has notbeen treated in a refinery, distilled, and/or fractionally distilled;(b) comprises components having a carbon number above 4, and the crudefeed has at least 0.5 grams of such components per gram of crude feed;(c) comprises hydrocarbons of which a portion has: a boiling rangedistribution below 100° C. at 0.101 MPa, a boiling range distributionbetween 100° C. and 200° C. at 0.101 MPa, a boiling range distributionbetween about 200° C. and about 300° C. at 0.101 MPa, a boiling rangedistribution between about 300° C. and about 400° C. at 0.101 MPa, and aboiling range distribution between about 400° C. and about 700° C. at0.101 MPa; (d) has, per gram of crude feed: at least 0.001 grams ofhydrocarbons having a boiling range distribution below 100° C. at 0.101MPa, at least 0.001 grams of hydrocarbons having a boiling rangedistribution between 100° C. and 200° C. at 0.101 MPa, at least 0.001grams of hydrocarbons having a boiling range distribution between about200° C. and about 300° C. at 0.101 MPa, at least 0.001 grams ofhydrocarbons having a boiling range distribution between about 300° C.and about 400° C. at 0.101 MPa, and at least 0.001 grams of hydrocarbonshaving a boiling range distribution between about 400° C. and about 700°C. at 0.101 MPa; (e) has a TAN; (f) has from about 0.2-0.99 grams, about0.3-0.8 grams, or about 0.4-0.7 grams of residue per gram of crude feed;(g) comprises nickel, vanadium, iron, or mixtures thereof; (h) comprisessulfur; and/or (i) nitrogen containing hydrocarbons.

In some embodiments, the invention also provides, in combination withone or more of the above embodiments, the hydrogen source that: (a) isgaseous; (b) comprises molecular hydrogen; (c) comprises lighthydrocarbons; (d) comprises methane, ethane, propane, or mixturesthereof; (e) comprises water; and/or (f) mixtures thereof.

In some embodiments, the invention also provides, in combination withone or more of the above embodiments, a method that includesconditioning the inorganic salt catalyst, wherein conditions theinorganic catalyst comprises: (a) heating the inorganic salt catalyst toa temperature of at least 300° C.; and/or (b) heating the inorganic saltcatalyst to a temperature of at least 300° C. and cooling the inorganicsalt catalyst to a temperature of at most 500° C.

In some embodiments, the invention also provides, in combination withone or more of the above embodiments, a method that comprises contactinga crude feed with one or more catalysts and controlling contactingconditions: (a) such that during the contacting at most 0.2 grams, atmost 0.15 grams, at most 0.1 grams, or at most 0.05 grams ofhydrocarbons that are not condensable at 25° C. and 0.101 MPa are formedper gram of crude feed, as determined by mass balance; (b) such that acontacting temperature is in a range from about 250-750° C. or betweenabout 260-550° C.; (c) a pressure is in a range from about 0.1-20 MPa;(d) such that a ratio of a gaseous hydrogen source to the crude feed isin a range from about 1-16100 or about 5-320 normal cubic meters of thehydrogen source per cubic meter of the crude feed; (e) to inhibit cokeformation; (f) to inhibit formation of coke in the total product or inthe crude feed during the contacting; (g) such that the crude productalso has at most 0.05 grams, at most 0.03 grams, at most 0.01 grams, orat most 0.003 grams of coke per gram of crude product; (h) such that atleast a portion of the inorganic salt catalyst is semi-liquid or liquidat such contacting conditions; (i) such that the crude product has a TANof at most 90% of the TAN of the crude feed; (j) such that the crudeproduct has a total Ni/V/Fe content of at most 90%, at most 50%, or atmost 10% of the Ni/V/Fe content of the crude feed; (k) such that thecrude product has a sulfur content of at most 90%, at most 60%, or atmost 30% of the sulfur content of the crude feed; (l) such that thecrude product has a nitrogen content of at most 90%, at most 70%, atmost 50%, or at most 10% of the nitrogen content of the crude feed; (m)such that the crude product has a residue content of at most 30%, atmost 10%, or at most 5% of the residue content of the crude feed; (n)such that ammonia is co-produced with the crude product; (o) such thatthe crude product comprises methanol, and the method further comprises:recovering the methanol from the crude product; combining the recoveredmethanol with additional crude feed to form an additional crudefeed/methanol mixture; and heating the additional crude feed/methanolmixture such that TAN of the additional crude feed is reduced to below1; (p) such that one or more properties of the crude product change byat most 90% relative to the respective one or more properties of thecrude feed; (q) such that an amount of catalyst in the contacting zoneranges from about 1-60 grams of total catalyst per 100 grams of crudefeed; and/or (r) such that a hydrogen source is added to the crude feedprior to or during the contacting.

In some embodiments, the invention also provides, in combination withone or more of the above embodiments, contacting conditions thatcomprise: (a) mixing the inorganic salt catalyst with the crude feed ata temperature below 500° C., wherein the inorganic salt catalyst issubstantially insoluble in the crude feed; (b) agitating the inorganiccatalyst in the crude feed; and/or (c) contacting the crude feed withthe inorganic salt catalyst in the presence of water and/or steam toproduce a total product that includes the crude product that is a liquidmixture at STP.

In some embodiments, the invention also provides, in combination withone or more of the above embodiments, a method that comprises contactinga crude feed with an inorganic salt catalyst and that further comprises:(a) providing steam to a contacting zone prior to or during contacting;(b) forming an emulsion of the crude feed with water prior to contactingthe crude feed with the inorganic salt catalyst and the hydrogen source;(c) spraying the crude feed into the contacting zone; and/or (d)contacting steam with the inorganic salt catalyst to at least partiallyremove coke from the surface of the inorganic salt catalyst.

In some embodiments, the invention also provides, in combination withone or more of the above embodiments, a method that comprises contactinga crude feed with an inorganic salt catalyst to produce a total productwherein at least a portion of the total product is produced as a vapor,and the method further comprises condensing at least a portion of thevapor at 25° C. and 0.101 MPa to form the crude product, the contactingconditions are controlled such that: (a) the crude product furthercomprises components with a selected boiling range distribution; and/or(b) the crude product comprises components having a selected APIgravity.

In some embodiments, the invention also provides, in combination withone or more of the above embodiments, a method that comprises contactinga crude feed with an one or more catalysts and that the one or morecatalysts are nonacidic.

In some embodiments, the invention also provides, in combination withone or more of the above embodiments, a K₃Fe₁₀S₁₄ catalyst or atransition metal sulfide catalyst that: (a) has a total of at least 0.4grams, at least 0.6 grams, or at least 0.8 grams of at least one oftransition metal sulfides per gram of the K₃Fe₁₀S₁₄ catalyst or thetransition metal sulfide catalyst; (b) has an atomic ratio of transitionmetal to sulfur in the K₃Fe₁₀S₁₄ catalyst or the transition metalsulfide catalyst in a range from about 0.2 to about 20; (c) furthercomprises one or more alkali metals, one or more compounds of one ormore alkali metals, or mixtures thereof; (d) further comprises one ormore alkaline-earth metals, one or more compounds of one or morealkaline-earth metals, or mixtures thereof; (e) further comprises one ormore alkali metals, one or more compounds of one or more alkali metals,or mixtures thereof, wherein an atomic ratio of transition metal tosulfur in the K₃Fe₁₀S₁₄ catalyst or the transition metal sulfidecatalyst is in a range from about 0.5-2.5 and an atomic ratio of thealkali metals to the transition metal is in a range from above 0 toabout 1; (f) further comprises one or more alkaline-earth metals, one ormore compounds of one or more alkaline-earth metals, or mixturesthereof, an atomic ratio of transition metal to sulfur in the K₃Fe₁₀S₁₄catalyst or the transition metal sulfide catalyst is in a range fromabout 0.5-2.5; and an atomic ratio of the alkaline-earth metal to thetransition metal is in a range from above 0 to about 1; (g) furthercomprises zinc; (h) further comprises KFe₂S₃; (i) further comprisesKFeS₂; and/or (j) is nonacidic.

In some embodiments, the transition metal sulfide catalyst comprises amixture of one or more transition metal sulfides, one or more alkalimetals, one or more compounds of one or more alkali metals, or mixturesthereof, and during contacting a portion of the transition metalsulfides are convert to K₃Fe₁₀S₁₄.

In some embodiments, the invention also provides, in combination withone or more of the above embodiments, one or more of the transitionmetal sulfides that or in which: (a) comprise one or more transitionmetals from Columns 6-10 of the Periodic Table, one or more compounds ofone or more transition metals from Columns 6-10, or mixtures thereof;(b) comprise one or more iron sulfides; (c) comprises FeS; (d) comprisesFeS₂; (e) comprise a mixture of iron sulfides, wherein the iron sulfidesare represented by the formula Fe_((1-b))S, where b is in a range fromabove 0 to about 0.17; (f) further comprises K₃Fe₁₀S₁₄ after contactwith the crude feed; (g) at least one of the transition metals of theone or more transition metal sulfides is iron; and/or (h) are depositedon a support, and the transition metal sulfide catalyst has at most 0.25grams of total support per 100 grams of catalyst.

In some embodiments, the invention also provides, in combination withone or more of the above embodiments, a method of forming a transitionmetal sulfide catalyst composition the method comprising mixing atransition metal oxide and a metal salt to form a transition metaloxide/metal salt mixture; reacting the transition metal oxide/metal saltmixture with hydrogen to form an intermediate; and reacting theintermediate with sulfur in the presence of one or more hydrocarbons toproduce the transition metal sulfide catalyst: (a) in which thetransition metal oxide/metal salt mixture comprises a hydrate; (b) themetal salt comprises an alkali metal carbonate; (c) that furthercomprises dispersing the intermediate in the one or more liquidhydrocarbons while it is reacted with the sulfur; (d) in which one ormore of the hydrocarbons have a boiling point of at least 100° C.; (e)in which one or more of the hydrocarbons is VGO, xylene, or mixturesthereof; (f) in which mixing the transition metal oxide and the metalsalt comprises: mixing the transition metal oxide and the metal salt inthe presence of de-ionized water to from a wet paste; drying the wetpaste at a temperature in a range from about 150-250° C.; and calciningthe dried paste at a temperature in a range from about 300-600° C.; (g)in which reacting the intermediate with sulfur comprises heating theintermediate in the presence of at least one of the hydrocarbons to atemperature in the range from about 240-350° C.; and/or (h) that furthercomprises contacting the catalyst composition with a crude feed thatcomprises sulfur and a hydrogen source.

In some embodiments, the invention also provides, in combination withone or more of the above embodiments, an inorganic salt catalyst thatcomprises: (a) one or more alkali metal carbonates, one or morealkaline-earth metal carbonates, or mixtures thereof; (b) one or morealkali metal hydroxides, one or more alkaline-earth metal hydroxides, ormixtures thereof; (c) one or more alkali metal hydrides, one or morealkaline-earth metal hydrides, or mixtures thereof; (d) one or moresulfides of one or more alkali metals, one or more sulfides of one ormore alkaline-earth metals, or mixtures thereof; (e) one or more amidesof one or more alkali metals, one or more amides of one or morealkaline-earth metals, or mixtures thereof; (f) one or more metals fromColumns 6-10 of the Periodic Table, one or more compounds of one or moremetals from Columns 6-10 of the Periodic Table, or mixtures thereof; (g)one or more inorganic metal salts, and wherein at least one of theinorganic metal salts generates hydride during use of the catalyst; (h)sodium, potassium, rubidium, cesium, or mixtures thereof; (i) calciumand/or magnesium; (j) a mixture of a sodium salt and a potassium saltand the potassium salt comprises potassium carbonate, potassiumhydroxide, potassium hydride, or mixtures thereof, and the sodium saltcomprises sodium carbonate, sodium hydroxide, sodium hydride, ormixtures thereof; and/or (k) mixtures thereof.

In some embodiments, the invention also provides, in combination withone or more of the above embodiments, an inorganic salt catalyst thatincludes alkali metals in which:(a) the atomic ratio of an alkali metalhaving an atomic number of at least 11 to an alkali metal having anatomic number greater than 11 is in a range from about 0.1 to about 4;(b) at least two of the alkali metals are sodium and potassium and anatomic ratio of sodium to potassium is in a range from about 0.1 toabout 4; (c) at least three of the alkali metals are sodium, potassium,and rubidium, and each of the atomic ratios of sodium to potassium,sodium to rubidium, and potassium to rubidium is in a range from about0.1 to about 5; (d) at least three of the alkali metals are sodium,potassium, and cesium, and each of the atomic ratios of sodium topotassium, sodium to cesium, and potassium to cesium is in a range fromabout 0.1 to about 5; (e) at least three of the alkali metals arepotassium, cesium, rubidium, and each of the atomic ratios of potassiumto cesium, potassium to rubidium, and cesium to rubidium is in a rangefrom about 0.1 to about 5.

In some embodiments, the invention also provides, in combination withone or more of the above embodiments, an inorganic salt catalystcomprising a support material, and: (a) the support material compriseszirconium oxide, calcium oxide, magnesium oxide, titanium oxide,hydrotalcite, alumina, germania, iron oxide, nickel oxide, zinc oxide,cadmium oxide, antimony oxide, or mixtures thereof; and/or (b)incorporated in the support material are: one or more metals fromColumns 6-10 of the Periodic Table, one or more compounds of one or moremetals from Columns 6-10 of the Periodic Table; one or more alkali metalcarbonates, one or more alkali metal hydroxides, one or more alkalimetal hydrides, one or more alkaline-earth metal carbonates, one or morealkaline-earth metal hydroxides, one or more alkaline-earth metalhydrides, and/or mixtures thereof.

In some embodiments, the invention also provides, in combination withone or more of the above embodiments, a method comprises contacting acrude feed with an inorganic salt catalyst that: (a) the catalyticactivity of the inorganic salt catalyst is substantially unchanged inthe presence of sulfur; and/or (b) the inorganic salt catalyst iscontinuously added to the crude feed.

In some embodiments, the invention also provides, in combination withone or more of the above embodiments, an inorganic salt catalyst thatexhibits: (a) an emitted gas inflection in a TAP temperature range, andthe emitted gas comprises water vapor and/or carbon dioxide; (b) a heattransition in a temperature range between about 200-500° C., about250-450° C., or about 300-400° C., as determined by differentialscanning calorimetry, at a heating rate of about 10° C. per minute; (c)a DSC temperature in a range between about 200-500° C., or about250-450° C.; (d) at a temperature of at least 100° C., an x-raydiffraction pattern that is broader than an x-ray diffraction pattern ofthe inorganic salt catalyst below 100° C.; and/or (e) afterconditioning, ionic conductivity, at 300° C., that is less than ionicconductivity of the inorganic salt catalyst before conditioning.

In some embodiments, the invention also provides, in combination withone or more of the above embodiments, an inorganic salt catalyst thatexhibits an emitted inflection in a temperature range, as determined byTAP, and the contacting conditions are also controlled such that acontacting temperature is: (a) above T₁, wherein T₁ is 30° C., 20° C.,or 10° C. below the TAP temperature of the inorganic salt catalyst; (b)at or above a TAP temperature; and/or (c) at least the TAP temperatureof the inorganic salt catalyst.

In some embodiments, the invention also provides, in combination withone or more of the above embodiments, an inorganic salt catalyst that orin which: (a) is liquid or semi-liquid at least at the TAP temperatureof the inorganic salt catalyst, and the inorganic salt catalyst issubstantially insoluble in the crude feed at least at the TAPtemperature, wherein the TAP temperature is the minimum temperature atwhich the inorganic salt catalyst exhibits an emitted gas inflection;(b) is a mixture of a liquid phase and a solid phase at a temperature ina range from about 50° C. to about 500° C.; and/or (c) at least one ofthe two inorganic salts has a DSC temperature above 500° C.

In some embodiments, the invention also provides, in combination withone or more of the above embodiments, an inorganic salt catalyst thatwhen tested in the form of particles that can pass through a 1000 micronfilter, self-deforms under gravity and/or under a pressure of at least0.007 MPa when heated to a temperature of at least 300° C., such thatthe inorganic salt catalyst transforms from a first form to a secondform, and the second form is incapable of returning to the first formupon cooling of the inorganic salt catalyst to about 20° C.

In some embodiments, the invention also provides, in combination withone or more of the above embodiments, an inorganic salt catalyst thathas, per gram of inorganic salt catalyst: (a) at most 0.01 grams oflithium, or compounds of lithium, calculated as the weight of lithium;(b) at most 0.001 grams of halide, calculated as the weight of halogen;and/or (c) at most 0.001 grams of glassy oxide compounds.

In some embodiments, the invention also provides, in combination withone or more of the above embodiments, the total product that has atleast 0.8 grams of crude product per gram of total product.

In some embodiments, the invention also provides, in combination withone or more of the above embodiments, a crude product that: (a) has atmost 0.003 grams, at most 0.02 grams, at most 0.01 grams, at most 0.05grams, most 0.001 grams, from about 0.000001-0.1 grams, about0.00001-0.05 grams, or about 0.0001-0.03 grams of residue per gram ofcrude product; (b) has from about 0 grams to about 0.05 grams, about0.00001-0.03 grams, or about 0.0001-0.01 grams of coke per gram of crudeproduct; (c) has an olefins content of at least 10% greater than theolefins content of the crude feed; (d) has greater than 0 grams, butless than 0.01 grams of total inorganic salt catalyst per gram of crudeproduct, as determined by mass balance; (e) has at least 0.1 grams, fromabout 0.00001-0.99 grams, from 0.04-0.9 grams from about 0.6-0.8 gramsof VGO per gram of crude product; (f) comprises VGO and the VGO has atleast 0.3 grams of aromatics per gram of VGO; (g) has 0.001 grams orfrom about 0.1-0.5 grams of distillate; (h) an atomic H/C of at most1.4; (i) has an atomic H/C of about 90-110% of the H/C of the crudefeed; (j) has a monocyclic ring aromatic content of at least 10% greaterthan the monocyclic ring aromatic content of the crude feed; (k) hasmonocyclic ring aromatics that comprise xylenes, ethylbenzene orcompounds of ethylbenzene; (l) has, per gram of crude product, at most0.1 grams of benzene, from about 0.05-0.15 grams of toluene, from about0.3-0.9 grams of meta-xylene, from about 0.5-0.15 grams of ortho-xylene,and from about 0.2-0.6 grams of para-xylene; (m) has at least 0.0001grams or from about 0.01-0.5 grams of diesel; (n) comprises diesel, andthe diesel has at least 0.3 grams of aromatics per gram of diesel; (o)has at least 0.001 grams, from above 0 to about 0.7 grams, or from about0.001-0.5 grams of kerosene; (p) comprises kerosene, and the kerosenehas at least 0.2 grams or at least 0.5 grams of aromatics per gram ofkerosene, and/or a freezing point at a temperature of at most −30° C.,at most −40° C., or at most −50° C.; (q) has at least 0.001 grams or atleast 0.5 grams of naphtha; (r) comprises naphtha, and the naphtha hasat most 0.01 grams, at most 0.05 grams, or at most 0.002 grams ofbenzene per gram of naphtha, an octane number of at least 70, at least80, or at least 90, and/or iso-paraffins and normal paraffins with aweight ratio of iso-paraffins to normal paraffins in the naphtha of atmost 1.4; and/or (s) has a volume that is at least 10% greater than thevolume of the crude feed.

In some embodiments, the invention also provides, in combination withone or more of the above embodiments, a method that comprises contactinga crude feed with a catalyst to form a total product that comprises acrude product, further comprising: (a) combining the crude product witha crude that is the same or different from the crude feed to form ablend suitable for transporting; (b) combining the crude product with acrude that is the same or different from the crude feed to form a blendsuitable for treatment facilities; (c) fractionating the crude product;(d) fractionating the crude product into one or more distillatefractions, and producing transportation fuel from at least one of thedistillate fractions; and/or (e) when the catalyst is a transition metalsulfide catalyst, treating the transition metal sulfide catalyst torecover metals from the transition metal sulfide catalyst.

In some embodiments, the invention also provides, in combination withone or more of the above embodiments, a crude composition that has, pergram of composition: (a) at least 0.001 grams of VGO, and the VGO has atleast 0.3 grams of aromatics per gram of VGO; (b) at least 0.001 gramsof diesel, and the diesel has at least 0.3 grams of aromatics per gramof diesel; (c) at least 0.001 grams of naphtha, and the naphtha: havingat most 0.5 grams of benzene per gram of naphtha, an octane number of atleast 70, and/or iso-paraffins and n-paraffins with a weight ratio ofthe iso-paraffins to the n-paraffins of at most 1.4; (d) a total of atleast 0.001 grams of a mixture of components that have a boiling rangedistribution of at most 204° C. (about 400° F.), and the mixture havingat most 0.15 grams of olefins per gram of mixture; (e) a weight ratio ofatomic hydrogen to atomic carbon in the composition of at most 1.75, orat most 1.8; (f) at least 0.001 grams of kerosene, and the kerosene has:at least 0.5 grams of aromatics per gram of kerosene and/or has afreezing point at a temperature of at most −30° C.; (g) from about0.09-0.13 grams of atomic hydrogen per gram of composition; (h)non-condensable hydrocarbon gases and naphtha, which, when combined,have at most 0.15 grams of olefins per gram of the combinednon-condensable hydrocarbon gases and naphtha; (i) non-condensablehydrocarbon gases and naphtha, which, when combined, compriseiso-paraffins and n-paraffins with a weight ratio of the iso-paraffinsto the n-paraffins in the combined naphtha and non-condensablehydrocarbon gases of at most 1.4; (j) the hydrocarbons with a carbonnumber of up to 3 comprising: olefins and paraffins with carbon numbersof 2 (C₂) and 3 (C₃), and a weight ratio of the combined C₂ and C₃olefins to the combined C₂ and C₃ paraffins is at most 0.3; olefins andparaffins with a carbon number of 2 (C₂), wherein a weight ratio of theC₂ olefins to the C₂ paraffins is at most 0.2; and/or olefins andparaffins with a carbon number of 3 (C₃), wherein a weight ratio of theC₃ olefins to the C₃ paraffins is at most 0.3; (k) has butadiene contentof at least 0.005 grams; (l) has an API graving in a range from about 15to about 30 at 15.5° C.; (m) has at most 0.00001 grams of total Ni/V/Feper gram of composition; (n) a paraffins content of the hydrocarbonshaving a boiling range distribution of at most 204° C. in a range fromabout 0.7-0.98 grams; (o) hydrocarbons with a boiling range distributionof at most 204° C. that have, per gram of olefins hydrocarbons having aboiling range distribution of at most 204° C., from about 0.001-0.5grams of olefins (p) hydrocarbons with a boiling range distribution ofat most 204° C. that comprise olefins, and the olefins have at least0.001 grams of terminal olefins per gram of olefins; (q) hydrocarbonswith a boiling range distribution of at most 204° C. that compriseolefins, and the olefins have a molar ratio of terminal olefins tointernal olefins of at least 0.4; and/or (r) from about 0.001-0.5 gramsof olefins per gram of hydrocarbons in a boiling range distributionbetween about 20° C. and about 204° C.

In some embodiments, the invention also provides, in combination withone or more of the above embodiments, a crude composition that has atleast one of the catalysts comprising one or more alkali metals, inwhich: (a) at least one of the alkali metals is potassium, rubidium; orcesium, or mixtures thereof; and/or (b) at least one of the catalystsfurther comprises a transition metal, a transition metal sulfide and/orbartonite.

In further embodiments, features from specific embodiments may becombined with features from other embodiments. For example, featuresfrom the any one of the series of embodiments may be combined withfeatures from any of the other series of embodiments.

In further embodiments, crude products are obtainable by any of themethods and systems described herein.

In further embodiments, additional features may be added to the specificembodiments described herein.

BRIEF DESCRIPTION OF THE DRAWINGS

Advantages of the present invention will become apparent to thoseskilled in the art with the benefit of the following detaileddescription and upon reference to the accompanying drawings in which:

FIG. 1 is a schematic of an embodiment of a contacting system forcontacting the crude feed with a hydrogen source in the presence of oneor more catalysts to produce the total product.

FIG. 2 is a schematic of another embodiment of a contacting system forcontacting the crude feed with a hydrogen source in the presence of oneor more catalysts to produce the total product.

FIG. 3 is a schematic of an embodiment of a separation zone incombination with a contacting system.

FIG. 4 is a schematic of an embodiment of a blending zone in combinationwith a contacting system.

FIG. 5 is a schematic of an embodiment of a separation zone, acontacting system, and a blending zone.

FIG. 6 is a schematic of an embodiment of multiple contacting systems.

FIG. 7 is a schematic of an embodiment of an ionic conductivitymeasurement system.

FIG. 8 is a tabulation of properties of the crude feed and properties ofcrude products obtained from embodiments of contacting the crude feedwith the transition metal sulfide catalyst.

FIG. 9 is a tabulation of compositions of the crude feed andcompositions of non-condensable hydrocarbons obtained from embodimentsof contacting the crude feed with the transition metal sulfide catalyst.

FIG. 10 is a tabulation of properties and compositions of crude productsobtained from embodiments of contacting the crude feed with thetransition metal sulfide catalyst.

FIG. 11 is a graphical representation of log 10 plots of ion currents ofemitted gases of an inorganic salt catalyst versus temperature, asdetermined by TAP.

FIG. 12 is a graphic representation of log plots of the resistance ofinorganic salt catalysts and an inorganic salt relative to theresistance of potassium carbonate versus temperature.

FIG. 13 is a graphic representation of log plots of the resistance of aNa₂CO₃/K₂CO₃/Rb₂CO₃ catalyst relative to resistance of the potassiumcarbonate versus temperature.

FIG. 14 is a graphical representation of weight percent of coke, liquidhydrocarbons, and gas versus various hydrogen sources produced fromembodiments of contacting the crude feed with the inorganic saltcatalyst.

FIG. 15 is a graphical representation of weight percentage versus carbonnumber of crude products produced from embodiments of contacting thecrude feed with the inorganic salt catalyst.

FIG. 16 is a tabulation of components produced from embodiments ofcontacting the crude feed with inorganic salt catalysts, a metal salt,or silicon carbide.

While the invention is susceptible to various modifications andalternative forms, specific embodiments thereof are shown by way ofexample in the drawings and will herein be described in detail. Thedrawings may not be to scale. It should be understood that the drawingsand detailed description thereto are not intended to limit the inventionto the particular form disclosed, but on the contrary, the intention isto cover all modifications, equivalents, and alternatives falling withinthe spirit and scope of the present invention.

DETAILED DESCRIPTION OF THE INVENTION

Certain embodiments of the inventions are described herein in moredetail. Terms used herein are defined as follows.

“Alkali metal(s)” refer to one or more metals from Column 1 of thePeriodic Table, one or more compounds of one or more metals from Column1 of the Periodic Table, or mixtures thereof.

“Alkaline-earth metal(s)” refer to one or more metals from Column 2 ofthe Periodic Table, one or more compounds of one or more metals fromColumn 2 of the Periodic Table, or mixtures thereof.

“AMU” refers to atomic mass unit.

“ASTM” refers to American Standard Testing and Materials.

“C₅ asphaltenes” refer to asphaltenes that are insoluble in pentane. C₅asphaltenes content is as determined by ASTM Method D2007.

Atomic hydrogen percentage and atomic carbon percentage of crude feed,crude product, naphtha, kerosene, diesel, and VGO are as determined byASTM Method D5291.

“API gravity” refers to API gravity at 15.5° C. API gravity is asdetermined by ASTM Method D6822.

“Bitumen” refers to one type of crude produced and/or retorted from ahydrocarbon formation.

Boiling range distributions for the crude feed and/or total product areas determined by ASTM Methods D5307, unless otherwise mentioned. Contentof hydrocarbon components, for example, paraffins, iso-paraffins,olefins, naphthenes and aromatics in naphtha are as determined by ASTMMethod D6730. Content of aromatics in diesel and VGO is as determined byIP Method 368/90. Content of aromatics in kerosene is as determined byASTM Method D5186.

“Brønsted-Lowry acid” refers to a molecular entity with the ability todonate a proton to another molecular entity.

“Brønsted-Lowry base” refers to a molecular entity that is capable ofaccepting protons from another molecular entity. Examples ofBrønsted-Lowry bases include hydroxide (OH⁻), water (H₂O), carboxylate(RCO₂ ⁻), halide (Br⁻, Cl⁻, F⁻, I⁻), bisulfate (HSO₄ ⁻), and sulfate(SO₄ ²⁻).

“Carbon number” refers to the total number of carbon atoms in amolecule.

“Coke” refers to solids containing carbonaceous solids that are notvaporized under process conditions. The content of coke is as determinedby mass balance. The weight of coke is the total weight of solid minusthe total weight of input catalysts.

“Content” refers to the weight of a component in a substrate (forexample, a crude feed, a total product, or a crude product) expressed asweight fraction or weight percentage based on the total weight of thesubstrate. “Wtppm” refers to parts per million by weight.

“Diesel” refers to hydrocarbons with a boiling range distributionbetween 260° C. and 343° C. (500-650° F.) at 0.101 MPa. Diesel contentis as determined by ASTM Method D2887.

“Distillate” refers to hydrocarbons with a boiling range distributionbetween 204° C. and 343° C. (400-650° F.) at 0.101 MPa. Distillatecontent is as determined by ASTM Method D2887. Distillate may includekerosene and diesel.

“DSC” refers to differential scanning calorimetry.

“Freeze point” and “freezing point” refer to the temperature at whichformation of crystalline particles occurs in a liquid. A freezing pointis as determined by ASTM D2386.

“GC/MS” refers to gas chromatography in combination with massspectrometry.

“Hard base” refers to anions as described by Pearson in Journal ofAmerican Chemical Society, 1963, 85, p. 3533, which is incorporated byreference herein.

“H/C” refers to a weight ratio of atomic hydrogen to atomic carbon. H/Cis as determined from the values measured for weight percentage ofhydrogen and weight percentage of carbon by ASTM Method D5291.

“Heteroatoms” refer to oxygen, nitrogen, and/or sulfur contained in themolecular structure of a hydrocarbon. Heteroatoms content is asdetermined by ASTM Methods E385 for oxygen, D5762 for nitrogen, andD4294 for sulfur.

“Hydrogen source” refers to hydrogen, and/or a compound and/or compoundswhen in the presence of a crude feed and the catalyst react to providehydrogen to one or more compounds in the crude feed. A hydrogen sourcemay include, but is not limited to, hydrocarbons (for example, C₁ to C₆hydrocarbons such as methane, ethane, propane, butane, pentane,naphtha), water, or mixtures thereof. A mass balance is conducted toassess the net amount of hydrogen provided to one or more compounds inthe crude feed.

“Inorganic salt” refers to a compound that is composed of a metal cationand an anion.

“IP” refers to the Institute of Petroleum, now the Energy Institute ofLondon, United Kingdom.

“Iso-paraffins” refer to branched-chain saturated hydrocarbons.

“Kerosene” refers to hydrocarbons with a boiling range distributionbetween about 204° C. and about 260° C. (400-500° F.) at 0.101 MPa.Kerosene content is as determined by ASTM Method D2887.

“Lewis acid” refers to a compound or a material with the ability toaccept one or more electrons from another compound.

“Lewis base” refers to a compound and/or material with the ability todonate one or more electrons to another compound.

“Light Hydrocarbons” refer to hydrocarbons having carbon numbers in arange from 1 to 6.

“Liquid mixture” refers to a composition that includes one or morecompounds that are liquid at standard temperature and pressure (25° C.,0.101 MPa, hereinafter referred to as “STP”), or a composition thatincludes a combination of one or more compounds that are liquid at STPwith one or more compounds that are solid at STP.

“Micro-Carbon Residue” (“MCR”) refers to a quantity of carbon residueremaining after evaporation and pyrolysis of a substance. MCR content isas determined by ASTM Method D4530.

“Naphtha” refers to hydrocarbon components with a boiling rangedistribution between 38° C. and 204° C. (100-400° F.) at 0.101 MPa.Naphtha content is as determined by ASTM Method D2887.

“Ni/V/Fe” refers to nickel, vanadium, iron, or combinations thereof.

“Ni/V/Fe content” refers to Ni/V/Fe content in a substrate. Ni/V/Fecontent is as determined by ASTM Method D5863.

“Nm³/m³” refers to normal cubic meters of gas per cubic meter of crudefeed.

“Nonacidic” refers to Lewis base and/or Brønsted-Lowry base properties.

“Non-condensable gas” refers to components and/or a mixture ofcomponents that are gases at standard temperature and pressure (25° C.,0.101 MPa, hereinafter referred to as “STP”).

“n-Paraffins” refer to normal (straight chain) saturated hydrocarbons.

“Octane number” refers to a calculated numerical representation of theantiknock properties of a motor fuel compared to a standard referencefuel. A calculated octane number of naphtha is as determined by ASTMMethod D6730.

“Olefins” refer to compounds with non-aromatic carbon-carbon doublebonds. Types of olefins include, but are not limited to, cis, trans,terminal, internal, branched, and linear.

“Periodic Table” refers to the Periodic Table as specified by theInternational Union of Pure and Applied Chemistry (IUPAC), November2003.

“Polyaromatic compounds” refer to compounds that include two or morearomatic rings. Examples of polyaromatic compounds include, but are notlimited to, indene, naphthalene, anthracene, phenanthrene,benzothiophene, and dibenzothiophene.

“Residue” refers to components that have a boiling range distributionabove 538° C. (1000° F.) at 0.101 MPa, as determined by ASTM MethodD5307.

“Semiliquid” refers to a phase of a substance that has properties of aliquid phase and a solid phase of the substance. Examples of semiliquidinorganic salt catalysts include a slurry and/or a phase that has aconsistency of, for example, taffy, dough, or toothpaste.

“SCFB” refers to standard cubic feet of gas per barrel of crude feed.

“Superbase” refers to a material that can deprotonate hydrocarbons suchas paraffins and olefins under reaction conditions.

“TAN” refers to a total acid number expressed as milligrams (“mg”) ofKOH per gram (“g”) of sample. TAN is as determined by ASTM Method D664.

“TAP” refers to temporal-analysis-of-products.

“TMS” refers to transition metal sulfide.

“VGO” refers to components with a boiling range distribution betweenabout 343° C. and about 538° C. (650-1000° F.) at 0.101 MPa. VGO contentis as determined by ASTM Method D2887.

All referenced methods are incorporated herein by reference. In thecontext of this application, it is to be understood that if the valueobtained for a property of the composition tested is outside of thelimits of the test method, the test method may be recalibrated to testfor such property. It should be understood that other standardizedtesting methods that are considered equivalent to the referenced testingmethods may be used.

Crudes may be produced and/or retorted from hydrocarbon containingformations and then stabilized. Crudes are generally solid, semi-solid,and/or liquid. Crudes may include crude oil. Stabilization may include,but is not limited to, removal of non-condensable gases, water, salts,or combinations thereof, from the crude to form a stabilized crude. Suchstabilization may often occur at, or proximate to, the production and/orretorting site.

Stabilized crudes typically have not been distilled and/or fractionallydistilled in a treatment facility to produce multiple components withspecific boiling range distributions (for example, naphtha, distillates,VGO, and/or lubricating oils). Distillation includes, but is not limitedto, atmospheric distillation methods and/or vacuum distillation methods.Undistilled and/or unfractionated stabilized crudes may includecomponents that have a carbon number above 4 in quantities of at least0.5 grams of components per gram of crude. Examples of stabilized crudesinclude whole crudes, topped crudes, desalted crudes, desalted toppedcrudes, or combinations thereof. “Topped” refers to a crude that hasbeen treated such that at least some of the components that have aboiling point below 35° C. at 0.101 MPa are removed. Typically, toppedcrudes have a content of at most 0.1 grams, at most 0.05 grams, or atmost 0.02 grams of such components per gram of the topped crude.

Some stabilized crudes have properties that allow the stabilized crudesto be transported to conventional treatment facilities by transportationcarriers (for example, pipelines, trucks, or ships). Other crudes haveone or more unsuitable properties that render them disadvantaged.Disadvantaged crudes may be unacceptable to a transportation carrier,and/or a treatment facility, thus imparting a low economic value to thedisadvantaged crude. The economic value may be such that a reservoirthat includes the disadvantaged crude that is deemed too costly toproduce, transport, and/or treat.

Properties of disadvantaged crudes may include, but are not limited to:a) TAN of at least 0.5; b) viscosity of at least about 0.2 Pa·s; c) APIgravity of at most 19; d) a total Ni/V/Fe content of at least 0.00005grams or at least 0.0001 grams of Ni/V/Fe per gram of crude; e) a totalheteroatoms content of at least 0.005 grams of heteroatoms per gram ofcrude; f) a residue content of at least 0.01 grams of residue per gramof crude; g) an asphaltenes content of at least 0.04 grams ofasphaltenes per gram of crude; h) a MCR content of at least 0.02 gramsof MCR per gram of crude; or i) combinations thereof. In someembodiments, disadvantaged crude may include, per gram of disadvantagedcrude, at least 0.2 grams of residue, at least 0.3 grams of residue, atleast 0.5 grams of residue, or at least 0.9 grams of residue. In certainembodiments, disadvantaged crude has about 0.2-0.99 grams, about 0.3-0.9grams, or about 0.4-0.7 grams of residue per gram of disadvantagedcrude. In certain embodiments, disadvantaged crudes, per gram ofdisadvantaged crude, may have a sulfur content of at least 0.001 grams,at least 0.005 grams, at least 0.01 grams, or at least 0.02 grams.

Disadvantaged crudes may include a mixture of hydrocarbons having arange of boiling points. Disadvantaged crudes may include, per gram ofdisadvantaged crude: at least 0.001 grams, at least 0.005 grams, or atleast 0.01 grams of hydrocarbons with a boiling range distributionbetween about 200° C. and about 300° C. at 0.101 MPa; at least 0.001grams, at least 0.005 grams, or at least 0.01 grams of hydrocarbons witha boiling range distribution between about 300° C. and about 400° C. at0.101 MPa; and at least 0.001 grams, at least 0.005 grams, or at least0.01 grams of hydrocarbons with a boiling range distribution betweenabout 400° C. and about 700° C. at 0.101 MPa, or combinations thereof.

In some embodiments, disadvantaged crudes may also include, per gram ofdisadvantaged crude, at least 0.001 grams, at least 0.005 grams, or atleast 0.01 grams of hydrocarbons with a boiling range distribution of atmost 200° C. at 0.101 MPa in addition to higher boiling components.Typically, the disadvantaged crude has, per gram of disadvantaged crude,a content of such hydrocarbons of at most 0.2 grams, or at most 0.1grams.

In certain embodiments, disadvantaged crudes may include, per gram ofdisadvantaged crude, up to 0.9 grams, or up to 0.99 grams ofhydrocarbons with a boiling range distribution of at least 300° C. Incertain embodiments, disadvantaged crudes may also include, per gram ofdisadvantaged crude, at least 0.001 grams of hydrocarbons with a boilingrange distribution of at least 650° C. In certain embodiments,disadvantaged crudes may include, per gram of disadvantaged crude, up toabout 0.9 grams, or up to about 0.99 grams of hydrocarbons with aboiling range distribution between about 300° C. and about 1000° C.

Examples of disadvantaged crudes that can be treated using the processesdescribed herein include, but are not limited to, crudes from thefollowing countries and regions of those countries: Canadian Alberta,Venezuelan Orinoco, U.S. southern Californian and north slope Alaska,Mexico Bay of Campeche, Argentinean San Jorge basin, Brazilian Santosand Campos basins, China Bohai Gulf, China Karamay, Iraq Zagros,Kazakhstan Caspian, Nigeria Offshore, United Kingdom North Sea,Madagascar northwest, Oman, and Netherlands Schoonebek.

Treatment of disadvantaged crudes may enhance the properties of thedisadvantaged crudes such that the crudes are acceptable fortransportation and/or treatment. A crude and/or disadvantaged crude thatis to be treated may be referred to as “crude feed”. The crude feed maybe topped as described herein. The crude product resulting fromtreatment of the crude feed, using methods described herein, is suitablefor transporting and/or refining. Properties of the crude product arecloser to the corresponding properties of West Texas Intermediate crudethan the crude feed, or closer to the corresponding properties of Brentcrude than the crude feed, and thereby have enhanced economic valuerelative to the economic value of the crude feed. Such crude product maybe refined with less or no pre-treatment, thereby enhancing refiningefficiencies. Pre-treatment may include desulfurization,demetallization, and/or atmospheric distillation to remove impuritiesfrom the crude product.

Methods of contacting a crude feed in accordance with inventions aredescribed herein. Additionally, embodiments to produce products withvarious concentrations of naphtha, kerosene, diesel, and/or VGO, whichare not generally produced in conventional types of processes, aredescribed.

The crude feed may be contacted with a hydrogen source in the presenceof one or more of the catalysts in a contacting zone and/or incombinations of two or more contacting zones.

In some embodiments, the hydrogen source is generated in situ. In situgeneration of the hydrogen source may include the reaction of at least aportion of the crude feed with the inorganic salt catalyst attemperatures in a range from about 200-500° C. or about 300-400° C. toform hydrogen and/or light hydrocarbons. In situ generation of hydrogenmay include the reaction of at least a portion of the inorganic saltcatalyst that includes, for example, alkali metal formate.

The total product generally includes gas, vapor, liquids, or mixturesthereof produced during the contacting. The total product includes thecrude product that is a liquid mixture at STP and, in some embodiments,hydrocarbons that are not condensable at STP. In some embodiments, thetotal product and/or the crude product may include solids (such asinorganic solids and/or coke). In certain embodiments, the solids may beentrained in the liquid and/or vapor produced during contacting.

A contacting zone typically includes a reactor, a portion of a reactor,multiple portions of a reactor, or multiple reactors. Examples ofreactors that may be used to contact a crude feed with a hydrogen sourcein the presence of catalyst include a stacked bed reactor, a fixed bedreactor, a continuously stirred tank reactor (CSTR), a spray reactor, aplug-flow reactor, and a liquid/liquid contactor. Examples of a CSTRinclude a fluidized bed reactor and an ebullating bed reactor.

Contacting conditions typically include temperature, pressure, crudefeed flow, total product flow, residence time, hydrogen source flow, orcombinations thereof. Contacting conditions may be controlled to producea crude product with specified properties.

Contacting temperatures may range from about 200-800° C., about 300-700°C., or about 400-600° C. In embodiments in which the hydrogen source issupplied as a gas (for example, hydrogen gas, methane, or ethane), aratio of the gas to the crude feed will generally range from about 1-16,100 Nm³/m³, about 2-8000 Nm³/m³, about 3-4000 Nm³/m³, or about 5-320Nm³/m³. Contacting typically takes place in a pressure range betweenabout 0.1-20 MPa, about 1-16 MPa, about 2-10 MPa, or about 4-8 MPa. Insome embodiments in which steam is added, a ratio of steam to crude feedis in a range from about 0.01-3 kilograms, about 0.03-2.5 kilograms, orabout 0.1-1 kilogram of steam, per kilogram of crude feed. A flow rateof crude feed may be sufficient to maintain the volume of crude feed inthe contacting zone of at least 10%, at least 50%, or at least 90% ofthe total volume of the contacting zone. Typically, the volume of crudefeed in the contacting zone is about 40%, about 60%, or about 80% of thetotal volume of the contacting zone. In some embodiments, contacting maybe done in the presence of an additional gas, for example, argon,nitrogen, methane, ethane, propanes, butanes, propenes, butenes, orcombinations thereof.

FIG. 1 is a schematic of an embodiment of contacting system 100 used toproduce the total product as a vapor. The crude feed exits crude feedsupply 101 and enters contacting zone 102 via conduit 104. A quantity ofthe catalyst used in the contacting zone may range from about 1-100grams, about 2-80 grams, about 3-70 grams, or about 4-60 grams, per 100grams of crude feed in the contacting zone. In certain embodiments, adiluent may be added to the crude feed to lower the viscosity of thecrude feed. In some embodiments, the crude feed enters a bottom portionof contacting zone 102 via conduit 104. In certain embodiments, thecrude feed may be heated to a temperature of at least 100° C. or atleast 300° C. prior to and/or during introduction of the crude feed tocontacting zone 102. Typically, the crude feed may be heated to atemperature in a range from about 100-500° C. or about 200-400° C.

In some embodiments, the catalyst is combined with the crude feed andtransferred to contacting zone 102. The crude feed/catalyst mixture maybe heated to a temperature of at least 100° C. or at least 300° C. priorto introduction into contacting zone 102. Typically, the crude feed maybe heated to a temperature in a range from about 200-500° C. or about300-400° C. In some embodiments, the crude feed/catalyst mixture is aslurry. In certain embodiments, TAN of the crude feed may be reducedprior to introduction of the crude feed into the contacting zone. Forexample, when the crude feed/catalyst mixture is heated at a temperaturein a range from about 100-400° C. or about 200-300° C., alkali salts ofacidic components in the crude feed may be formed. The formation ofthese alkali salts may remove some acidic components from the crude feedto reduce the TAN of the crude feed.

In some embodiments, the crude feed is added continuously to contactingzone 102. Mixing in contacting zone 102 may be sufficient to inhibitseparation of the catalyst from the crude feed/catalyst mixture. Incertain embodiments, at least a portion of the catalyst may be removedfrom contacting zone 102, and in some embodiments, such catalyst isregenerated and re-used. In certain embodiments, fresh catalyst may beadded to contacting zone 102 during the reaction process.

In some embodiments, the crude feed and/or a mixture of crude feed withthe inorganic salt catalyst is introduced into the contacting zone as anemulsion. The emulsion may be prepared by combining an inorganic saltcatalyst/water mixture with a crude feed/surfactant mixture. In someembodiments, a stabilizer is added to the emulsion. The emulsion mayremain stable for at least 2 days, at least 4 days, or at least 7 days.Typically, the emulsion may remain stable for 30 days, 10 days, 5 days,or 3 days. Surfactants include, but are not limited to, organicpolycarboxylic acids (Tenax 2010; MeadWestvaco Specialty Product Group;Charleston, S.C., U.S.A.), C₂₁ dicarboxylic fatty acid (DIACID 1550;MeadWestvaco Specialty Product Group), petroleum sulfonates (HostapurSAS 30; Clarient Corporation, Charlotte, N.C., U.S.A.), Tergital NP-40Surfactant (Union Carbide; Danbury, Conn., U.S.A.), or mixtures thereof.Stabilizers include, but are not limited to, diethyleneamine (AldrichChemical Co.; Milwaukee, Wis., U.S.A.) and/or monoethanolamine (J. T.Baker; Phillipsburg, N.J., U.S.A.).

Recycle conduit 106 may couple conduit 108 and conduit 104. In someembodiments, recycle conduit 106 may directly enter and/or exitcontacting zone 102. Recycle conduit 106 may include flow control valve110. Flow control valve 110 may allow at least a portion of the materialfrom conduit 108 to be recycled to conduit 104 and/or contacting zone102. In some embodiments, a condensing unit may be positioned in conduit108 to allow at least a portion of the material to be condensed andrecycled to contacting zone 102. In certain embodiments, recycle conduit106 may be a gas recycle line. Flow control valves 110 and 110′ may beused to control flow to and from contacting zone 102 such that aconstant volume of liquid in the contacting zone is maintained. In someembodiments, a substantially selected volume range of liquid can bemaintained in the contacting zone 102. A volume of feed in contactingzone 102 may be monitored using standard instrumentation. Gas inlet port112 may be used to allow addition of the hydrogen source and/oradditional gases to the crude feed as the crude feed enters contactingzone 102. In some embodiments, steam inlet port 114 may be used to allowaddition of steam to contacting zone 102. In certain embodiments, anaqueous stream is introduced into contacting zone 102 through steaminlet port 114.

In some embodiments, at least a portion of the total product is producedas vapor from contacting zone 102. In certain embodiments, the totalproduct is produced as vapor and/or a vapor containing small amounts ofliquids and solids from the top of contacting zone 102. The vapor istransported to separation zone 116 via conduit 108. The ratio of ahydrogen source to crude feed in contacting zone 102 and/or the pressurein the contacting zone may be changed to control the vapor and/or liquidphase produced from the top of contacting zone 102. In some embodiments,the vapor produced from the top of contacting zone 102 includes at least0.5 grams, at least 0.8 grams, at least 0.9 grams, or at least 0.97grams of crude product per gram of crude feed. In certain embodiments,the vapor produced from the top of contacting zone 102 includes fromabout 0.8-0.99 grams, or about 0.9-0.98 grams of crude product per gramof crude feed.

Used catalyst and/or solids may remain in contacting zone 102 asby-products of the contacting process. The solids and/or used catalystmay include residual crude feed and/or coke.

In separation unit 116, the vapor is cooled and separated to form thecrude product and gases using standard separation techniques. The crudeproduct exits separation unit 116 and enters crude product receiver 119via conduit 118. The resulting crude product may be suitable fortransportation and/or treatment. Crude product receiver 119 may includeone or more pipelines, one or more storage units, one or moretransportation vessels, or combinations thereof. In some embodiments,the separated gas (for example, hydrogen, carbon monoxide, carbondioxide, hydrogen sulfide, or methane) is transported to otherprocessing units (for example, for use in a fuel cell or a sulfurrecovery plant) and/or recycled to contacting zone 102 via conduit 120.In certain embodiments, entrained solids and/or liquids in the crudeproduct may be removed using standard physical separation methods (forexample, filtration, centrifugation, or membrane separation).

FIG. 2 depicts contacting system 122 for treating crude feed with one ormore catalysts to produce a total product that may be a liquid, or aliquid mixed with gas or solids. The crude feed may enter contactingzone 102 via conduit 104. In some embodiments, the crude feed isreceived from the crude feed supply. Conduit 104 may include gas inletport 112. In some embodiments, gas inlet port 112 may directly entercontacting zone 102. In certain embodiments, steam inlet port 114 may beused to allow addition of the steam to contacting zone 102. The crudefeed may be contacted with the catalyst in contacting zone 102 toproduce a total product. In some embodiments, conduit 106 allows atleast a portion of the total product to be recycled to contacting zone102. A mixture that includes the total product and/or solids and/orunreacted crude feed exits contacting zone 102 and enters separationzone 124 via conduit 108. In some embodiments, a condensing unit may bepositioned (for example, in conduit 106) to allow at least a portion ofthe mixture in the conduit to be condensed and recycled to contactingzone 102 for further processing. In certain embodiments, recycle conduit106 may be a gas recycle line. In some embodiments, conduit 108 mayinclude a filter for removing particles from the total product.

In separation zone 124, at least a portion of the crude product may beseparated from the total product and/or catalyst. In embodiments inwhich the total product includes solids, the solids may be separatedfrom the total product using standard solid separation techniques (forexample, centrifugation, filtration, decantation, membrane separation).Solids include, for example, a combination of catalyst, used catalyst,and/or coke. In some embodiments, a portion of the gases is separatedfrom the total product. In some embodiments, at least a portion of thetotal product and/or solids may be recycled to conduit 104 and/or, insome embodiments, to contacting zone 102 via conduit 126. The recycledportion may, for example, be combined with the crude feed and entercontacting zone 102 for further processing. The crude product may exitseparation zone 124 via conduit 128. In certain embodiments, the crudeproduct may be transported to the crude product receiver.

In some embodiments, the total product and/or crude product may includeat least a portion of the catalyst. Gases entrained in the total productand/or crude product may be separated using standard gas/liquidseparation techniques, for example, sparging, membrane separation, andpressure reduction. In some embodiments, the separated gas istransported to other processing units (for example, for use in a fuelcell, a sulfur recovery plant, other processing units, or combinationsthereof) and/or recycled to the contacting zone.

In some embodiments, separation of at least a portion of a crude feed isperformed before the crude feed enters the contacting zone. FIG. 3 is aschematic of an embodiment of a separation zone in combination with acontacting system. Contacting system 130 may be contacting system 100and/or contacting system 122 (shown in FIGS. 1 and 2). The crude feedenters separation zone 132 via conduit 104. In separation zone 132, atleast a portion of the crude feed is separated using standard separationtechniques to produce a separated crude feed and hydrocarbons. Theseparated crude feed, in some embodiments, includes a mixture ofcomponents with a boiling range distribution of at least 100° C., atleast 120° C. or, in some embodiments, a boiling range distribution ofat least 200° C. Typically, the separated crude feed includes a mixtureof components with a boiling range distribution between about 100-1000°C., about 120-900° C., or about 200-800° C. The hydrocarbons separatedfrom the crude feed exit separation zone 132 via conduit 134 to betransported to other processing units, treatment facilities, storagefacilities, or combinations thereof.

At least a portion of the separated crude feed exits separation zone 132and enters contacting system 130 via conduit 136 to be further processedto form the crude product, which exits contacting system 130 via conduit138.

In some embodiments, the crude product produced from a crude feed by anymethod described herein is blended with a crude that is the same as ordifferent from the crude feed. For example, the crude product may becombined with a crude having a different viscosity thereby resulting ina blended product having a viscosity that is between the viscosity ofthe crude product and the viscosity of the crude. The resulting blendedproduct may be suitable for transportation and/or treatment.

FIG. 4 is a schematic of an embodiment of a combination of blending zone140 and contacting system 130. In certain embodiments, at least aportion of the crude product exits contacting system 130 via conduit 138and enters blending zone 140. In blending zone 140, at least a portionof the crude product is combined with one or more process streams (forexample, a hydrocarbon stream produced from separation of one or morecrude feeds, or naphtha), a crude, a crude feed, or mixtures thereof, toproduce a blended product. The process streams, crude feed, crude, ormixtures thereof, are introduced directly into blending zone 140 orupstream of the blending zone via conduit 142. A mixing system may belocated in or near blending zone 140. The blended product may meetspecific product specifications. Specific product specificationsinclude, but are not limited to, a range of or a limit of API gravity,TAN, viscosity, or combinations thereof. The blended product exitsblending zone 140 via conduit 144 to be transported and/or processed.

In some embodiments, methanol is generated during the contacting processusing the catalyst. For example, hydrogen and carbon monoxide may reactto form methanol. The recovered methanol may contain dissolved salts,for example, potassium hydroxide. The recovered methanol may be combinedwith additional crude feed to form a crude feed/methanol mixture.Combining methanol with the crude feed tends to lower the viscosity ofthe crude feed. Heating the crude feed/methanol mixture to at most 500°C. may reduce TAN of the crude feed to less than 1.

FIG. 5 is a schematic of an embodiment of a separation zone incombination with a contacting system in combination with a blendingzone. The crude feed enters separation zone 132 through conduit 104. Thecrude feed is separated as previously described to form a separatedcrude feed. The separated crude feed enters contacting system 130through conduit 136. The crude product exits contacting system 130 andenters blending zone 140 through conduit 138. In blending zone 140,other process stream and/or crudes introduced via conduit 142 arecombined with the crude product to form a blended product. The blendedproduct exits blending zone 140 via conduit 144.

FIG. 6 is a schematic of multiple contacting system 146. Contactingsystem 100 (shown in FIG. 1) may be positioned before contacting system148. In an alternate embodiment, the positions of the contacting systemscan be reversed. Contacting system 100 includes an inorganic saltcatalyst. Contacting system 148 may include one or more catalysts. Thecatalyst in contacting system 148 may be an additional inorganic saltcatalyst, the transition metal sulfide catalyst, commercial catalysts,or mixtures thereof. The crude feed enters contacting system 100 viaconduit 104 and is contacted with a hydrogen source in the presence ofthe inorganic salt catalyst to produce the total product. The totalproduct includes hydrogen and, in some embodiments, a crude product. Thetotal product may exit contacting system 100 via conduit 108. Thehydrogen generated from contact of the inorganic salt catalyst with thecrude feed may be used as a hydrogen source for contacting system 148.At least a portion of the generated hydrogen is transferred tocontacting system 148 from contacting system 100 via conduit 150.

In an alternate embodiment, such generated hydrogen may be separatedand/or treated, and then transferred to contacting system 148 viaconduit 150. In certain embodiments, contacting system 148 may be a partof contacting system 100 such that the generated hydrogen flows directlyfrom contacting system 100 to contacting system 148. In someembodiments, a vapor stream produced from contacting system 100 isdirectly mixed with the crude feed entering contacting system 148.

A second crude feed enters contacting system 148 via conduit 152. Incontacting system 148, contact of the crude feed with at least a portionof the generated hydrogen and the catalyst produces a product. Theproduct is, in some embodiments, the total product. The product exitscontacting system 148 via conduit 154.

In certain embodiments, a system that includes contacting systems,contacting zones, separation zones, and/or blending zones, as shown inFIGS. 1-6, may be located at or proximate to a production site thatproduces disadvantaged crude feed. After processing through thecatalytic system, the crude feed may be considered suitable fortransportation and/or for use in a refinery process.

In some embodiments, the crude product and/or the blended product aretransported to a refinery and/or a treatment facility. The crude productand/or the blended product may be processed to produce commercialproducts such as transportation fuel, heating fuel, lubricants, orchemicals. Processing may include distilling and/or fractionallydistilling the crude product and/or blended product to produce one ormore distillate fractions. In some embodiments, the crude product, theblended product, and/or the one or more distillate fractions may behydrotreated.

The total product includes, in some embodiments, at most 0.05 grams, atmost 0.03 grams, or at most 0.01 grams of coke per gram of totalproduct. In certain embodiments, the total product is substantially freeof coke (that is, coke is not detectable). In some embodiments, thecrude product may include at most 0.05 grams, at most 0.03 grams, atmost 0.01 grams, at most 0.005 grams, or at most 0.003 grams of coke pergram of crude product. In certain embodiments, the crude product has acoke content in a range from above 0 to about 0.05, about 0.00001-0.03grams, about 0.0001-0.01 grams, or about 0.001-0.005 grams per gram ofcrude product, or is not detectable.

In certain embodiments, the crude product has an MCR content that is atmost 90%, at most 80%, at most 50%, at most 30%, or at most 10% of theMCR content of the crude feed. In some embodiments, the crude producthas a negligible MCR content. In some embodiments, the crude producthas, per gram of crude product, at most 0.05 grams, at most 0.03 grams,at most 0.01 grams, or at most 0.001 grams of MCR. Typically, the crudeproduct has from about 0 grams to about 0.04 grams, about 0.000001-0.03grams, or about 0.00001-0.01 grams of MCR per gram of crude product.

In some embodiments, the total product includes non-condensable gas. Thenon-condensable gas typically includes, but is not limited to, carbondioxide, ammonia, hydrogen sulfide, hydrogen, carbon monoxide, methane,other hydrocarbons that are not condensable at STP, or a mixturethereof.

In certain embodiments, hydrogen gas, carbon dioxide, carbon monoxide,or combinations thereof can be formed in situ by contact of steam andlight hydrocarbons with the inorganic salt catalyst. Typically, underthermodynamic conditions a molar ratio of carbon monoxide to carbondioxide is about 0.07. A molar ratio of the generated carbon monoxide tothe generated carbon dioxide, in some embodiments, is at least 0.3, atleast 0.5, or at least 0.7. In some embodiments, a molar ratio of thegenerated carbon monoxide to the generated carbon dioxide is in a rangefrom about 0.3-1.0, about 0.4-0.9, or about 0.5-0.8. The ability togenerate carbon monoxide preferentially to carbon dioxide in situ may bebeneficial to other processes located in a proximate area or upstream ofthe process. For example, the generated carbon monoxide may be used as areducing agent in treating hydrocarbon formations or used in otherprocesses, for example, syngas processes.

In some embodiments, the total product as produced herein may include amixture of compounds that have a boiling range distribution betweenabout −10° C. and about 538° C. The mixture may include hydrocarbonsthat have carbon numbers in a range from 1 to 4. The mixture may includefrom about 0.001-0.8 grams, about 0.003-0.1 grams, or about 0.005-0.01grams, of C₄ hydrocarbons per gram of such mixture. The C₄ hydrocarbonsmay include from about 0.001-0.8 grams, about 0.003-0.1 grams, or about0.005-0.01 grams of butadiene per gram of C₄ hydrocarbons. In someembodiments, iso-paraffins are produced relative to n-paraffins at aweight ratio of at most 1.5, at most 1.4, at most 1.0, at most 0.8, atmost 0.3, or at most 0.1. In certain embodiments, iso-paraffins areproduce relative to n-paraffins at a weight ratio in a range from about0.00001-1.5, about 0.0001-1.0, or about 0.001-0.1. The paraffins mayinclude iso-paraffins and/or n-paraffins.

In some embodiments, the total product and/or crude product may includeolefins and/or paraffins in ratios or amounts that are not generallyfound in crudes produced and/or retorted from a formation. The olefinsinclude a mixture of olefins with a terminal double bond (“alphaolefins”) and olefins with internal double bonds. In certainembodiments, the olefin content of the crude product is greater than theolefin content of the crude feed by a factor of about 2, about 10, about50, about 100, or at least 200. In some embodiments, the olefin contentof the crude product is greater than the olefin content of the crudefeed by a factor of at most 1,000, at most 500, at most 300, or at most250.

In certain embodiments, the hydrocarbons with a boiling rangedistribution between 20-400° C. have an olefins content in a range fromabout 0.00001-0.1 grams, about 0.0001-0.05 grams, or about 0.01-0.04grams per gram of hydrocarbons having a boiling range distribution in arange between 20-400° C.

In some embodiments, at least 0.001 grams, at least 0.005 grams, or atleast 0.01 grams of alpha olefins per gram of crude product may beproduced. In certain embodiments, the crude product has from about0.0001-0.5 grams, about 0.001-0.2 grams, or about 0.01-0.1 grams ofalpha olefins per gram of crude product. In certain embodiments, thehydrocarbons with a boiling range distribution between about 20-400° C.have an alpha olefins content in a range from about 0.0001-0.08 grams,about 0.001-0.05 grams, or about 0.01-0.04 grams per gram ofhydrocarbons with a boiling range distribution between about 20-400° C.

In some embodiments, the hydrocarbons with a boiling range distributionbetween 20-204° C. have a weight ratio of alpha olefins to internaldouble bond olefins of at least 0.7, at least 0.8, at least 0.9, atleast 1.0, at least 1.4, or at least 1.5. In some embodiments, thehydrocarbons with a boiling range distribution between 20-204° C. have aweight ratio of alpha olefins to internal double bond olefins in a rangefrom about 0.7-10, about 0.8-5, about 0.9-3, or about 1-2. A weightratio of alpha olefins to internal double bond olefins of the crudes andcommercial products is typically at most 0.5. The ability to produce anincreased amount of alpha olefins to olefins with internal double bondsmay facilitate the conversion of the crude product to commercialproducts.

In some embodiments, contact of a crude feed with a hydrogen source inthe presence of an inorganic salt catalyst may produce hydrocarbons witha boiling range distribution between 20-204° C. that include linearolefins. The linear olefins have cis and trans double bonds. A weightratio of linear olefins with trans double bonds to linear olefins withcis double bonds is at most 0.4, at most 1.0, or at most 1.4. In certainembodiments, the weight ratio of linear olefins with trans double bondsto linear olefins with cis double bonds is in a range from about0.001-1.4, about 0.01-1.0, or about 0.1-0.4.

In certain embodiments, hydrocarbons having a boiling range distributionin a range between 20-204° C. have a n-paraffins content of at least 0.1grams, at least 0.15 grams, at least 0.20 grams, or at least 0.30 gramsper gram of hydrocarbons having a boiling range distribution in a rangebetween 20-400° C. The n-paraffins content of such hydrocarbons, pergram of hydrocarbons, may be in a range from about 0.001-0.9 grams,about 0.1-0.8 grams, or about 0.2-0.5 grams. In some embodiments, suchhydrocarbons have a weight ratio of the iso-paraffins to the n-paraffinsof at most 1.5, at most 1.4, at most 1.0, at most 0.8, or at most 0.3.From the n-paraffins content in such hydrocarbons, the n-paraffinscontent of the crude product may be estimated to be in a range fromabout 0.001-0.9 grams, about 0.01-0.8 grams, or about 0.1-0.5 grams pergram of crude product.

In some embodiments, the crude product has a total Ni/V/Fe content of atmost 90%, at most 50%, at most 10%, at most 5%, or at most 3% of aNi/V/Fe content of the crude feed. In certain embodiments, the crudeproduct includes, per gram of crude product, at most 0.0001 grams, atmost 1×10⁻⁵ grams, or at most 1×10⁻⁶ grams of Ni/V/Fe. In certainembodiments, the crude product has, per gram of crude product, a totalNi/V/Fe content in a range from about 1×10⁻⁷ grams to about 5×10⁻⁵grams, about 3×10⁻⁷ grams to about 2×10⁻⁵ grams, or about 1×10⁻⁶ gramsto about 1×10⁻⁵ grams.

In some embodiments, the crude product has a TAN of at most 90%, at most50%, or at most 10% of the TAN of the crude feed. The crude product may,in certain embodiments, have a TAN of at most 1, at most 0.5, at most0.1, or at most 0.05. In some embodiments, TAN of the crude product maybe in a range from about 0.001 to about 0.5, about 0.01 to about 0.2, orabout 0.05 to about 0.1.

In certain embodiments, the API gravity of the crude product is at least10% higher, at least 50% higher, or at least 90% higher than the APIgravity of the crude feed. In certain embodiments, API gravity of thecrude product is between about 13-50, about 15-30, or about 16-20.

In some embodiments, the crude product has a total heteroatoms contentof at most 70%, at most 50%, or at most 30% of the total heteroatomscontent of the crude feed. In certain embodiments, the crude product hasa total heteroatoms content of at least 10%, at least 40%, or at least60% of the total heteroatoms content of the crude feed.

The crude product may have a sulfur content of at most 90%, at most 70%,or at most 60% of a sulfur content of the crude feed. The sulfur contentof the crude product, per gram of crude product, may be at most 0.02grams, at most 0.008 grams, at most 0.005 grams, at most 0.004 grams, atmost 0.003 grams, or at most 0.001 grams. In certain embodiments, thecrude product has, per gram of crude product, a sulfur content in arange from about 0.0001-0.02 grams or about 0.005-0.01 grams.

In certain embodiments, the crude product may have a nitrogen content ofat most 90% or at most 80% of a nitrogen content of the crude feed. Thenitrogen content of the crude product, per gram of crude product, may beat most 0.004 grams, at most 0.003 grams, or at most 0.001 grams. Insome embodiments, the crude product has, per gram of crude product, anitrogen content in a range from about 0.0001-0.005 grams, or about0.001-0.003 grams.

In some embodiments, the crude product has, per gram of crude product,from about 0.05-0.2 grams, or about 0.09-0.15 grams of hydrogen. The H/Cof the crude product may be at most 1.8, at most 1.7, at most 1.6, atmost 1.5, or at most 1.4. In some embodiments, the H/C of the crudeproduct is about 80-120%, or about 90-110% of the H/C of the crude feed.In other embodiments, the H/C of the crude product is about 100-120% ofthe H/C of the crude feed. A crude product H/C within 20% of the crudefeed H/C indicates that uptake and/or consumption of hydrogen in theprocess is minimal.

The crude product includes components with a range of boiling points. Insome embodiments, the crude product includes: at least 0.001 grams, orfrom about 0.001 to about 0.5 grams of hydrocarbons with a boiling rangedistribution of at most 200° C. or at most 204° C. at 0.101 MPa; atleast 0.001 grams, or from about 0.001 to about 0.5 grams ofhydrocarbons with a boiling range distribution between about 200° C. andabout 300° C. at 0.101 MPa; at least 0.001 grams, or from about 0.001 toabout 0.5 grams of hydrocarbons with a boiling range distributionbetween about 300° C. and about 400° C. at 0.101 MPa; and at least 0.001grams, or from about 0.001 to about 0.5 grams of hydrocarbons with aboiling range distribution between about 400° C. and about 538° C. at0.101 MPa.

In some embodiments, the crude product has, per gram of crude product, anaphtha content from about 0.00001-0.2 grams, about 0.0001-0.1 grams, orabout 0.001-0.05 grams. In certain embodiments, the crude product hasfrom 0.001-0.2 grams or 0.01-0.05 grams of naphtha. In some embodiments,the naphtha has at most 0.15 grams, at most 0.1 grams, or at most 0.05grams of olefins per gram of naphtha. The crude product has, in certainembodiments, from 0.00001-0.15 grams, 0.0001-0.1 grams, or 0.001-0.05grams of olefins per gram of crude product. In some embodiments, thenaphtha has, per gram of naphtha, a benzene content of at most 0.01grams, at most 0.005 grams, or at most 0.002 grams. In certainembodiments, the naphtha has a benzene content that is non-detectable,or in a range from about 1×10⁻⁷ grams to about 1×10⁻² grams, about1×10⁻⁶ grams to about 1×10⁻⁵ grams, about 5×10⁻⁶ grams to about 1×10⁻⁴grams. Compositions that contain benzene may be considered hazardous tohandle, thus a crude product that has a relatively low benzene contentmay not require special handling.

In certain embodiments, naphtha may include aromatic compounds. Aromaticcompounds may include monocyclic ring compounds and/or polycyclic ringcompounds. The monocyclic ring compounds may include, but are notlimited to, benzene, toluene, ortho-xylene, meta-xylene, para-xylene,ethyl benzene, 1-ethyl-3-methyl benzene; 1-ethyl-2-methyl benzene;1,2,3-trimethyl benzene; 1,3,5-trimethyl benzene; 1-methyl-3-propylbenzene; 1-methyl-2-propyl benzene; 2-ethyl-1,4-dimethyl benzene;2-ethyl-2,4-dimethyl benzene; 1,2,3,4-tetra-methyl benzene; ethyl,pentylmethyl benzene; 1,3 diethyl-2,4,5,6-tetramethyl benzene;tri-isopropyl-ortho-xylene; substituted congeners of benzene, toluene,ortho-xylene, meta-xylene, para-xylene, or mixtures thereof. Monocyclicaromatics are used in a variety of commercial products and/or sold asindividual components. The crude product produced as described hereintypically has an enhanced content of monocyclic aromatics.

In certain embodiments, the crude product has, per gram of crudeproduct, a toluene content from about 0.001-0.2 grams, about 0.05-0.15grams, or about 0.01-0.1 grams. The crude product has, per gram of crudeproduct, a meta-xylene content from about 0.001-0.1 grams, about0.005-0.09 grams, or about 0.05-0.08 grams. The crude product has, pergram of crude product, an ortho-xylene content from about 0.001-0.2grams, about 0.005-0.1 grams, or about 0.01-0.05 grams. The crudeproduct has, per gram of crude product, a para-xylene content from about0.001-0.09 grams, about 0.005-0.08 grams, or about 0.001-0.06 grams.

An increase in the aromatics content of naphtha tends to increase theoctane number of the naphtha. Crudes may be valued based on anestimation of a gasoline potential of the crudes. Gasoline potential mayinclude, but is not limited to, a calculated octane number for thenaphtha portion of the crudes. Crudes typically have calculated octanenumbers in a range of about 35-60. The octane number of gasoline tendsto reduce the requirement for additives that increase the octane numberof the gasoline. In certain embodiments, the crude product includesnaphtha that has an octane number of at least 60, at least 70, at least80, or at least 90. Typically, the octane number of the naphtha is in arange from about 60-99, about 70-98, or about 80-95.

In some embodiments, the crude product has a higher total aromaticscontent in hydrocarbons having a boiling range distribution between 204°C. and 500° C. (total “naphtha and kerosene”) relative to the totalaromatics content in the total naphtha and kerosene of the crude feed byat least 5%, at least 10%, at least 50%, or at least 99%. Typically, thetotal aromatics content in the total naphtha and kerosene of crude feedis about 8%, about 20%, about 75%, or about 100% greater than the totalaromatics content in the total naphtha and kerosene of the crude feed.

In some embodiments, the kerosene and naphtha may have a totalpolyaromatic compounds content in a range from about 0.00001-0.5 grams,about 0.0001-0.2 grams, or about 0.001-0.1 grams per gram of totalkerosene and naphtha.

The crude product has, per gram of crude product, a distillate contentin a range from about 0.0001-0.9 grams, from about 0.001-0.5 grams, fromabout 0.005-0.3 grams, or from about 0.01-0.2 grams. In someembodiments, a weight ratio of kerosene to diesel in the distillate, isin a range from about 1:4 to about 4:1, about 1:3 to about 3:1, or about2:5 to about 5:2.

In some embodiments, crude product has, per gram of crude product, atleast 0.001 grams, from above 0 to about 0.7 grams, about 0.001-0.5grams, or about 0.01-0.1 grams of kerosene. In certain embodiments, thecrude product has from 0.001-0.5 grams or 0.01-0.3 grams of kerosene. Insome embodiments, the kerosene has, per gram of kerosene, an aromaticscontent of at least 0.2 grams, at least 0.3 grams, or at least 0.4grams. In certain embodiments, the kerosene has, per gram of kerosene,an aromatics content in a range from about 0.1-0.5 grams, or from about0.2-0.4 grams.

In certain embodiments, a freezing point of the kerosene may be below−30° C., below −40° C., or below −50° C. An increase in the content ofaromatics of the kerosene portion of the crude product tends to increasethe density and reduce the freezing point of the kerosene portion of thecrude product. A crude product with a kerosene portion having a highdensity and low freezing point may be refined to produce aviationturbine fuel with the desirable properties of high density and lowfreezing point.

In certain embodiments, the crude product has, per gram of crudeproduct, a diesel content in a range from about 0.001-0.8 grams or fromabout 0.01-0.4 grams. In certain embodiments, the diesel has, per gramof diesel, an aromatics content of at least 0.1 grams, at least 0.3grams, or at least 0.5 grams. In some embodiments, the diesel has, pergram of diesel, an aromatics content in a range from about 0.1-1 grams,about 0.3-0.8 grams, or about 0.2-0.5 grams.

In some embodiments, the crude product has, per gram of crude product, aVGO content in a range from about 0.0001-0.99 grams, from about0.001-0.8 grams, or from about 0.1-0.3 grams. In certain embodiments,the VGO content in the crude product is in a range from 0.4-0.9 grams,or about 0.6-0.8 grams per gram of crude product. In certainembodiments, the VGO has, per gram of VGO, an aromatics content in arange from about 0.1-0.99 grams, about 0.3-0.8 grams, or about 0.5-0.6grams.

In some embodiments, the crude product has a residue content of at most70%, at most 50%, at most 30%, at most 10%, or at most 1% of the crudefeed. In certain embodiments, the crude product has, per gram of crudeproduct, a residue content of at most 0.1 grams, at most 0.05 grams, atmost 0.03 grams, at most 0.02 grams, at most 0.01 grams, at most 0.005grams, or at most 0.001 grams. In some embodiments, the crude producthas, per gram of crude product, a residue content in a range from about0.000001-0.1 grams, about 0.00001-0.05 grams, about 0.001-0.03 grams, orabout 0.005-0.04 grams.

In some embodiments, the crude product may include at least a portion ofthe catalyst. In some embodiments, a crude product includes from greaterthan 0 grams, but less than 0.01 grams, about 0.000001-0.001 grams, orabout 0.00001-0.0001 grams of catalyst per gram of crude product. Thecatalyst may assist in stabilizing the crude product duringtransportation and/or treatment in processing facilities. The catalystmay inhibit corrosion, inhibit friction, and/or increase waterseparation abilities of the crude product. A crude product that includesat least a portion of the catalyst may be further processed to producelubricants and/or other commercial products.

The catalyst used for treatment of a crude feed in the presence of ahydrogen source to produce the total product may be a single catalyst ora plurality of catalysts. The catalysts of the application may first bea catalyst precursor that is converted to the catalyst in the contactingzone when hydrogen and/or a crude feed containing sulfur is contactedwith the catalyst precursor.

The catalysts used in contacting the crude feed with a hydrogen sourceto produce the total product may assist in the reduction of themolecular weight of the crude feed. Not to be bound by theory, thecatalyst in combination with the hydrogen source may reduce a molecularweight of components in the crude feed through the action of basic(Lewis basic or Brønsted-Lowry basic) and/or superbasic components inthe catalyst. Examples of catalysts that may have Lewis base and/orBrønsted-Lowry base properties include catalysts described herein.

In some embodiments, the catalyst is a TMS catalyst. The TMS catalystincludes a compound that contains a transition metal sulfide. For thepurposes of this application, weight of the transition metal sulfide inthe TMS catalyst is determined by adding the total weight of thetransition metal(s) to the total weight of sulfur in the catalyst. Anatomic ratio of the transition metal to sulfur is typically in a rangefrom about 0.2-20, about 0.5-10, or about 1-5. Examples of transitionmetal sulfides may be found in “Inorganic Sulfur Chemistry”; Edited byG. Nickless; Elsevier Publishing Company; Amsterdam-London-New York;Copyright 1968; Chapter 19, which is incorporated herein by reference.

In certain embodiments, the TMS catalyst may include a total of at least0.4 grams, at least 0.5 grams, at least 0.8 grams, or at least 0.99grams of one or more transition metal sulfides per gram of catalyst. Incertain embodiments, the TMS catalyst has, per gram of catalyst, a totalcontent of one or more transition metal sulfides in a range from about0.4-0.999 grams, about 0.5-0.9 grams, or about 0.6-0.8 grams.

The TMS catalyst includes one or more transition metal sulfides.Examples of transition metal sulfides include pentlandite(Fe_(4.5)Ni_(4.5)S₈), smythite (Fe_(6.75)Ni_(2.25)S₁₁), bravoite(Fe_(0.7)Ni_(0.2)Co_(0.1)S₂), mackinawite (Fe_(0.75)Ni_(0.25)S_(0.9)),argentopentlandite (AgFe₆Ni₂S₈), isocubanite (CuFe₂S₃), isocalcopyrite(Cu₈Fe₉S₁₆), sphalerite (Zn_(0.95)Fe_(0.05)S), mooihoekite (Cu₉Fe₉S₁₆),chatkalite (Cu₆FeSn₂S₈), sternbergite (AgFe₂S₃), chalcopyrite (CuFeS₂),troilite (FeS), pyrite (FeS₂), pyrrhotite (Fe_((1-x))S (x=0 to 0.17)),heazlewoodite (Ni₃S₂) or vaesite (NiS₂).

In some embodiments, the TMS catalyst includes one or more transitionmetal sulfides in combination with alkali metal(s), alkaline-earthmetal(s), zinc, compounds of zinc, or mixtures thereof. The TMS catalystis, in some embodiments, represented by the general chemical formulaA_(c)[M_(a)S_(b)]_(d), in which A represents alkali metal,alkaline-earth metal or zinc; M represents a transition metal fromColumns 6-10 of the Periodic Table; and S is sulfur. An atomic ratio ofa to b is in a range from about 0.5 to about 2.5, or from about 1 toabout 2. An atomic ratio of c to a is in a range from 0.0001 to about 1,from about 0.1 to about 0.8, or from about 0.3 to about 0.5. In someembodiments, the transition metal is iron.

In some embodiments, the TMS catalyst may include generally known alkaliand/or alkaline-earth metals/transition metal sulfides (for example,bartonite (K₃Fe₁₀S₁₄), rasvumite (KFe₂S₃), djerfisherite(K₆NaFe₁₉Cu₄NiS₂₆Cl), chlorobartonite(K_(6.1)Fe₂₄Cu_(0.2)S_(26.1)Cl_(0.7)), and/or coyoteite(NaFe₃S₅.(H₂O)₂). In some embodiments, the TMS catalyst includesbartonite prepared in situ. Bartonite prepared in situ may be referredto as synthetic bartonite. Natural and/or synthetic bartonite may beused as a TMS catalyst in the methods described herein.

In some embodiments, the TMS catalyst may include at most 25 grams, atmost 15 grams, or at most 1 gram of support material per 100 grams ofthe TMS catalyst. Typically, the TMS catalyst has from 0 to about 25grams, about 0.00001 to about 20 grams, about 0.0001 grams to about 10grams of support material per 100 grams of the TMS catalyst. Examples ofsupport materials that may be used with the TMS catalyst includerefractory oxides, porous carbon materials, zeolites, or mixturesthereof. In some embodiments, the TMS catalyst is substantially free, orfree, of support materials.

The TMS catalyst that includes alkali metal(s), alkaline-earth metal(s),zinc, compounds of zinc, or mixtures thereof may contain one or moretransition metal sulfides, bimetallic alkali metal-transition metalsulfides, higher valence transition metal sulfides, transition metaloxides, or mixtures thereof, as determined using x-ray diffraction. Aportion of the alkali metal(s) component, alkaline-earth metal(s)component, zinc component and/or a portion of the transition metalsulfide component of the TMS catalyst may, in some embodiments, bepresent as an amorphous composition not detectable by x-ray diffractiontechniques.

In some embodiments, crystalline particles of the TMS catalyst and/ormixtures of crystalline particles of the TMS catalyst have a particlesize of at most 10⁸ Å, at most 10³ Å, at most 100 Å, or at most 40 Å. Innormal practice, the particle size of the crystalline particles of theTMS catalyst will generally be at least 10 Å.

The TMS catalyst that includes alkali metal(s), alkaline-earth metal(s),zinc, compounds of zinc, or mixtures thereof may be prepared by mixing asufficient amount of de-ionized water, a desired amount of a transitionmetal oxide, and desired amount of Columns 1-2 metal carbonate(s),Columns 1-2 metal oxalate(s), Columns 1-2 metal acetate(s), zinccarbonate, zinc acetate, zinc oxalate, or mixtures thereof to form a wetpaste. The wet paste may be dried at a temperature from about 100-300°C. or 150-250° C. to form a transition metal oxide/salt mixture. Thetransition metal oxide/salt mixture may be calcined at a temperatureranging from about 300-1000° C., about 500-800° C., or about 600-700° C.to form a transition metal oxide/metal salt mixture. The transitionmetal oxide/metal salt mixture may be reacted with hydrogen to form areduced intermediate solid. The addition of hydrogen may be performed ata flow rate sufficient to provide an excess amount of hydrogen to thetransition metal oxide/metal salt mixture. Hydrogen may be added overabout 10-50 hours or about 20-40 hours to the transition metaloxide/metal salt mixture to produce a reduced intermediate solid thatincludes elemental transition metal. Hydrogen addition may be performedat a temperature of about 35-500° C., about 50-400° C., or about100-300° C., and a total pressure of about 10-15 MPa, about 11-14 MPa,or about 12-13 MPa. It should be understood that reduction time,reaction temperature, selection of reducing gas, pressure of reducinggas, and/or flow rate of reducing gas used to prepare the intermediatesolid is often changed relative to the absolute mass of the selectedtransition metal oxide. The reduced intermediate solid may, in someembodiments, be passed through a 40-mesh sieve with minimal force.

The reduced intermediate solid may be incrementally added to a hot (forexample, about 100° C.) diluent/elemental sulfur, and/or one or morecompounds of sulfur, mixture at a rate to control the evolution of heatand production of gas. The diluent may include any suitable diluent thatprovides a means to dissipate the heat of sulfurization. The diluent mayinclude solvents with a boiling range distributions of at least 100° C.,at least 150° C., least 200° C., or at least 300° C. Typically thediluent has a boiling range distribution between about 100-500° C.,about 150-400° C., or about 200-300° C. In some embodiments, the diluentis VGO and/or xylenes. Sulfur compounds include, but are not limited to,hydrogen sulfide and/or thiols. An amount of sulfur and/or sulfurcompounds may range from 1-100 mole %, 2-80 mole %, 5-50 mole %, 10-30mole %, based on the moles of Columns 1-2 metal or zinc in the Columns1-2 metal salt or zinc salt. After addition of the reduced intermediatesolid to the diluent/elemental sulfur mixture, the resulting mixture maybe incrementally heated to a final temperature of about 200-500° C.,about 250-450° C., or about 300-400° C. and maintained at the finaltemperature for at least 1 hour, at least 2 hours, or at least 10 hours.Typically, the final temperature is maintained for about 15 hours, about10 hours, about 5 hours, or about 1.5 hours. After heating to theelevated sulfurizing reaction temperature, the diluent/catalyst mixturemay be cooled to a temperature in a range from about 0-100° C., about30-90° C., or about 50-80° C. to facilitate recovery of the catalystfrom the mixture. The sulfurized catalyst may be isolated in anoxygen-free atmosphere from the diluent using standard techniques andwashed with at least a portion of a low boiling solvent (for example,pentane, heptane, or hexane) to produce the TMS catalyst. The TMScatalyst may be powdered using standard techniques.

In some embodiments, the catalyst is an inorganic salt catalyst. Theanion of the inorganic salt catalyst may include an inorganic compound,an organic compound, or mixtures thereof. The inorganic salt catalystincludes alkali metal carbonates, alkali metal hydroxides, alkali metalhydrides, alkali metal amides, alkali metal sulfides, alkali metalacetates, alkali metal oxalates, alkali metal formates, alkali metalpyruvates, alkaline-earth metal carbonates, alkaline-earth metalhydroxides, alkaline-earth metal hydrides, alkaline-earth metal amides,alkaline-earth metal sulfides, alkaline-earth metal acetates,alkaline-earth metal oxalates, alkaline-earth metal formates,alkaline-earth metal pyruvates, or mixtures thereof.

Inorganic salt catalysts include, but are not limited to, mixtures of:NaOH/RbOH/CsOH; KOH/RbOH/CsOH; NaOH/KOH/RbOH; NaOH/KOH/CsOH;K₂CO₃/Rb₂CO₃/Cs₂CO₃; Na₂O/K₂O/K₂CO₃; NaHCO₃/KHCO₃/Rb₂CO₃;LiHCO₃/KHCO₃/Rb₂CO₃; KOH/RbOH/CsOH mixed with a mixture ofK₂CO₃/Rb₂CO₃/Cs₂CO₃; K₂CO₃/CaCO₃; K₂CO₃/MgCO₃; Cs₂CO₃/CaCO₃; Cs₂CO₃/CaO;Na₂CO₃/Ca(OH)₂; KH/CsCO₃; KOCHO/CaO; CsOCHO/CaCO₃; CsOCHO/Ca(OCHO)₂;NaNH₂/K₂CO₃/Rb₂O; K₂CO₃/CaCO₃/Rb₂CO₃; K₂CO₃/CaCO₃/Cs₂CO₃;K₂CO₃/MgCO₃/Rb₂CO₃; K₂CO₃/MgCO₃/Cs₂CO₃; or Ca(OH)₂ mixed with a mixtureof K₂CO₃/Rb₂CO₃/Cs₂CO₃.

In some embodiments, the inorganic salt catalyst contains at most0.00001 grams, at most 0.001 grams, or at most 0.01 grams of lithium,calculated as the weight of lithium, per gram of inorganic saltcatalyst. The inorganic salt catalyst has, in some embodiments, fromabout 0 but less than 0.01 grams, about 0.0000001-0.001 grams, or about0.00001-0.0001 grams of lithium, calculated as the weight of lithium,per gram of inorganic salt catalyst,

In certain embodiments, an inorganic salt catalyst includes one or morealkali metal salts that include an alkali metal with an atomic number ofat least 11. An atomic ratio of an alkali metal having an atomic numberof at least 11 to an alkali metal having an atomic number greater than11, in some embodiments, is in a range from about 0.1 to about 10, about0.2 to about 6, or about 0.3 to about 4 when the inorganic salt catalysthas two or more alkali metals. For example, the inorganic salt catalystmay include salts of sodium, potassium, and rubidium with the ratio ofsodium to potassium being in a range from about 0.1-6; the ratio ofsodium to rubidium being in a range from about 0.1-6; and the ratio ofpotassium to rubidium being in a range from about 0.1-6. In anotherexample, the inorganic salt catalyst includes a sodium salt and apotassium salt with the atomic ratio of sodium to potassium being in arange from about 0.1 to about 4.

In some embodiments, an inorganic salt catalyst also includes metalsfrom Columns 8-10 of the Periodic Table, compounds of metals fromColumns 8-10 of the Periodic Table, metals from Column 6 of the PeriodicTable, compounds of metals from Column 6 of the Periodic Table, ormixtures thereof. Metals from Columns 8-10 include, but are not limitedto, iron, ruthenium, cobalt, or nickel. Metals from Column 6 include,but are not limited to, chromium, molybdenum, or tungsten. In someembodiments, the inorganic salt catalyst includes about 0.1-0.5 grams,or about 0.2-0.4 grams of Raney nickel per gram of inorganic saltcatalyst.

In certain embodiments, the inorganic salt catalyst also includes metaloxides from Columns 1-2 and/or Column 13 of the Periodic Table. Metalsfrom Column 13 include, but are not limited to, boron or aluminum.Non-limiting examples of metal oxides include lithium oxide (Li₂O),potassium oxide (K₂O), calcium oxide (CaO), or aluminum oxide (Al₂O₃).

The inorganic salt catalyst is, in certain embodiments, free of orsubstantially free of Lewis acids (for example, BCl₃, AlCl₃, and SO₃),Brønsted-Lowry acids (for example, H₃O⁺, H₂SO₄, HCl, and HNO₃),glass-forming compositions (for example, borates and silicates), andhalides. The inorganic salt may contain, per gram of inorganic saltcatalyst: from about 0 grams to about 0.1 grams, about 0.000001-0.01grams, or about 0.00001-0.005 grams of: a) halides; b) compositions thatform glasses at temperatures of at least 350° C., or at most 1000° C.;c) Lewis acids; d) Brønsted-Lowry acids; or e) mixtures thereof.

The inorganic salt catalyst may be prepared using standard techniques.For example, a desired amount of each component of the catalyst may becombined using standard mixing techniques (for example, milling and/orpulverizing). In other embodiments, inorganic compositions are dissolvedin a solvent (for example, water or a suitable organic solvent) to forman inorganic composition/solvent mixture. The solvent may be removedusing standard separation techniques to produce the inorganic saltcatalyst.

In some embodiments, inorganic salts of the inorganic salt catalyst maybe incorporated into a support to form a supported inorganic saltcatalyst. Examples of supports include, but are not limited to,zirconium oxide, calcium oxide, magnesium oxide, titanium oxide,hydrotalcite, alumina, germania, iron oxide, nickel oxide, zinc oxide,cadmium oxide, antimony oxide, and mixtures thereof. In someembodiments, an inorganic salt, a Columns 6-10 metal and/or a compoundof a Columns 6-10 metal may be impregnated in the support.Alternatively, inorganic salts may be melted or softened with heat andforced in and/or onto a metal support or metal oxide support to form asupported inorganic salt catalyst.

A structure of the inorganic salt catalyst typically becomesnonhomogenous, permeable, and/or mobile at a determined temperature orin a temperature range when loss of order occurs in the catalyststructure. The inorganic salt catalyst may become disordered without asubstantial change in composition (for example, without decomposition ofthe salt). Not to be bound by theory, it is believed that the inorganicsalt catalyst becomes disordered (mobile) when distances between ions inthe lattice of the inorganic salt catalyst increase. As the ionicdistances increase, a crude feed and/or a hydrogen source may permeatethrough the inorganic salt catalyst instead of across the surface of theinorganic salt catalyst. Permeation of the crude feed and/or hydrogensource through the inorganic salt often results in an increase in thecontacting area between the inorganic salt catalyst and the crude feedand/or the hydrogen source. An increase in contacting area and/orreactivity area of the inorganic salt catalyst may often increase theyield of crude product, limit production of residue and/or coke, and/orfacilitate a change in properties in the crude product relative to thesame properties of the crude feed. Disorder of the inorganic saltcatalyst (for example, nonhomogeneity, permeability, and/or mobility)may be determined using DSC methods, ionic conductivity measurementmethods, TAP methods, visual inspection, x-ray diffraction methods, orcombinations thereof.

The use of TAP to determine characteristics of catalysts is described inU.S. Pat. Nos. 4,626,412 to Ebner et al.; 5,039,489 to Gleaves et al.;and 5,264,183 to Ebner et al., all of which are incorporated herein byreference. A TAP system may be obtained from Mithra Technologies (Foley,Mo., U.S.A.). The TAP analysis may be performed in a temperature rangefrom about 25-850° C., about 50-500° C., or about 60-400° C., at aheating rate in a range from about 10-50° C., or about 20-40° C., and ata vacuum in a range from about 1×10⁻¹³ to about 1×10⁻⁸ torr. Thetemperature may remain constant and/or increase as a function of time.As the temperature of the inorganic salt catalyst increases, gasemission from the inorganic salt catalyst is measured. Examples of gasesthat evolve from the inorganic salt catalyst include carbon monoxide,carbon dioxide, hydrogen, water, or mixtures thereof. The temperature atwhich an inflection (sharp increase) in gas evolution from the inorganicsalt catalyst is detected is considered to be the temperature at whichthe inorganic salt catalyst becomes disordered.

In some embodiments, an inflection of emitted gas from the inorganicsalt catalyst may be detected over a range of temperatures as determinedusing TAP. The temperature or the temperature range is referred to asthe “TAP temperature”. The initial temperature of the temperature rangedetermined using TAP is referred to as the “minimum TAP temperature”.

The emitted gas inflection exhibited by inorganic salt catalystssuitable for contact with a crude feed is in a TAP temperature rangefrom about 100-600° C., about 200-500° C., or about 300-400° C.Typically, the TAP temperature is in a range from about 300-500° C. Insome embodiments, different compositions of suitable inorganic saltcatalysts also exhibit gas inflections, but at different TAPtemperatures.

The magnitude of the ionization inflection associated with the emittedgas may be an indication of the order of the particles in a crystalstructure. In a highly ordered crystal structure, the ion particles aregenerally tightly associated, and release of ions, molecules, gases, orcombinations thereof, from the structure requires more energy (that ismore heat). In a disordered crystal structure, ions are not associatedto each other as strongly as ions in a highly ordered crystal structure.Due to the lower ion association, less energy is generally required torelease ions, molecules, and/or gases from a disordered crystalstructure, and thus, a quantity of ions and/or gas released from adisordered crystal structure is typically greater than a quantity ofions and/or gas released from a highly ordered crystal structure at aselected temperature.

In some embodiments, a heat of dissociation of the inorganic saltcatalyst may be observed in a range from about 50° C. to about 500° C.at a heating rate or cooling rate of about 10° C., as determined using adifferential scanning calorimeter. In a DSC method, a sample may beheated to a first temperature, cooled to room temperature, and thenheated a second time. Transitions observed during the first heatinggenerally are representative of entrained water and/or solvent and maynot be representative of the heat of dissociations. For example, easilyobserved heat of drying of a moist or hydrated sample may generallyoccur below 250° C., typically between 100-150° C. The transitionsobserved during the cooling cycle and the second heating correspond tothe heat of dissociation of the sample.

“Heat transition” refers to the process that occurs when orderedmolecules and/or atoms in a structure become disordered when thetemperature increases during the DSC analysis. “Cool transition” refersto the process that occurs when molecules and/or atoms in a structurebecome more homogeneous when the temperature decreases during the DSCanalysis. In some embodiments, the heat/cool transition of the inorganicsalt catalyst occurs over a range of temperatures that are detectedusing DSC. The temperature or temperature range at which the heattransition of the inorganic salt catalyst occurs during a second heatingcycle is referred to as “DSC temperature”. The lowest DSC temperature ofthe temperature range during a second heating cycle is referred to asthe “minimum DSC temperature”. The inorganic salt catalyst may exhibit aheat transition in a range between about 200-500° C., about 250-450° C.,or about 300-400° C.

In an inorganic salt that contains inorganic salt particles that are arelatively homogeneous mixture, a shape of the peak associated with theheat absorbed during a second heating cycle may be relatively narrow. Inan inorganic salt catalyst that contains inorganic salt particles in arelatively non-homogeneous mixture, the shape of the peak associatedwith heat absorbed during a second heating cycle may be relativelybroad. An absence of peaks in a DSC spectrum indicates that the saltdoes not absorb or release heat in the scanned temperature range. Lackof a heat transition generally indicates that the structure of thesample does not change upon heating.

As homogeneity of the particles of an inorganic salt mixture increases,the ability of the mixture to remain a solid and/or a semiliquid duringheating decreases. Homogeneity of an inorganic mixture may be related tothe ionic radius of the cations in the mixtures. For cations withsmaller ionic radii, the ability of a cation to share electron densitywith a corresponding anion increases and the acidity of thecorresponding anion increases. For a series of ions of similar charges,a smaller ionic radius results in higher interionic attractive forcesbetween the cation and the anion if the anion is a hard base. The higherinterionic attractive forces tend to result in higher heat transitiontemperatures for the salt and/or more homogeneous mixture of particlesin the salt (sharper peak and increased area under the DSC curve).Mixtures that include cations with small ionic radii tend to be moreacidic than cations of larger ionic radii, and thus acidity of theinorganic salt mixture increases with decreasing cationic radii. Forexample, contact of a crude feed with a hydrogen source in the presenceof an inorganic mixture that includes lithium cations tends to produceincreased quantities of gas and/or coke relative to contact of the crudefeed with a hydrogen source in the presence of an inorganic saltcatalyst that includes cations with a larger ionic radii than lithium.The ability to inhibit generation of gas and/or coke increases the totalliquid product yield of the process.

In certain embodiments, the inorganic salt catalyst may include two ormore inorganic salts. A minimum DSC temperature for each of theinorganic salts may be determined. The minimum DSC temperature of theinorganic salt catalyst may be below the minimum DSC temperature of atleast one of the inorganic metal salts in the inorganic salt catalyst.For example, the inorganic salt catalyst may include potassium carbonateand cesium carbonate. Potassium carbonate and cesium carbonate exhibitDSC temperatures greater than 500° C. A K₂CO₃/Rb₂CO₃/Cs₂CO₃ catalystexhibits a DSC temperature in a range from about 290-300° C.

In some embodiments, the TAP temperature may be between the DSCtemperature of at least one of the inorganic salts and the DSCtemperature of the inorganic salt catalyst. For example, the TAPtemperature of the inorganic salt catalyst may be in a range from about350-500° C. The DSC temperature of the same inorganic salt catalyst maybe in a range from about 200-300° C., and the DSC temperature of theindividual salts may be at least 500° C. or at most 1000° C.

An inorganic salt catalyst that has a TAP and/or DSC temperature betweenabout 150-500° C., about 200-450° C., or about 300-400° C., and does notundergo decomposition at these temperatures, in many embodiments, can beused to catalyze conversion of high molecular weight and/or highviscosity compositions (for example, crude feed) to liquid products.

In certain embodiments, the inorganic salt catalyst may exhibitincreased conductivity relative to individual inorganic salts duringheating of the inorganic salt catalyst in a temperature range from about200-600° C., about 300-500° C., or about 350-450° C. Increasedconductivity of the inorganic salt catalyst is generally attributed tothe particles in the inorganic salt catalyst becoming mobile. The ionicconductivity of some inorganic salt catalysts changes at a lowertemperature than the temperature at which ionic conductivity of a singlecomponent of the inorganic salt catalyst changes.

Ionic conductivity of inorganic salts may be determined by applyingOhm's law: V=IR, where V is voltage, I is current, and R is resistance.To measure ionic conductivity, the inorganic salt catalyst may be placedin a quartz vessel with two wires (for example, copper wires or platinumwires) separated from each other, but immersed in the inorganic saltcatalyst.

FIG. 7 is a schematic of a system that may be used to measure ionicconductivity. Quartz vessel 156 containing sample 158 may be placed in aheating apparatus and heated incrementally to a desired temperature.Voltage from source 160 is applied to wire 162 during heating. Theresulting current through wires 162 and 164 is measured at meter 166.Meter 166 may be, but is not limited to, a multimeter or a Wheatstonebridge. As sample 158 becomes less homogeneous (more mobile) withoutdecomposition occurring, the resistivity of the sample should decreaseand the observed current at meter 166 should increase.

In some embodiments, at a desired temperature, the inorganic saltcatalyst may have a different ionic conductivity after heating, cooling,and then heating. The difference in ionic conductivities may indicatethat the crystal structure of the inorganic salt catalyst has beenaltered from an original shape (first form) to a different shape (secondform) during heating. The ionic conductivities, after heating, areexpected to be similar or the same if the form of the inorganic saltcatalyst does not change during heating.

In certain embodiments, the inorganic salt catalyst has a particle sizein a range of about 10-1000 microns, about 20-500 microns, or about50-100 microns, as determined by passing the inorganic salt catalystthrough a mesh or a sieve.

The inorganic salt catalyst may soften when heated to temperatures above50° C. and below 500° C. As the inorganic salt catalyst softens, liquidsand catalyst particles may co-exist in the matrix of the inorganic saltcatalyst. The catalyst particles may, in some embodiments, self-deformunder gravity, or under a pressure of at least 0.007 MPa, or at most0.101 MPa, when heated to a temperature of at least 300° C., or at most800° C., such that the inorganic salt catalyst transforms from a firstform to a second form. Upon cooling of the inorganic salt catalyst toabout 20° C., the second form of the inorganic salt catalyst isincapable of returning to the first form of the inorganic salt catalyst.The temperature at which the inorganic salt transforms from the firstform to a second form is referred to as the “deformation” temperature.The deformation temperature may be a temperature range or a singletemperature. In certain embodiments, the particles of the inorganic saltcatalyst self-deform under gravity or pressure upon heating to adeformation temperature below the deformation temperature of any of theindividual inorganic metal salts. In some embodiments, an inorganic saltcatalyst includes two or more inorganic salts that have differentdeformation temperatures. The deformation temperature of the inorganicsalt catalyst differs, in some embodiments, from the deformationtemperatures of the individual inorganic metal salts.

In certain embodiments, the inorganic salt catalyst is liquid and/orsemiliquid at, or above, the TAP and/or DSC temperature. In someembodiments, the inorganic salt catalyst is a liquid or a semiliquid atthe minimum TAP and/or DSC temperature. At or above the minimum TAPand/or DSC temperature, liquid or semiliquid inorganic salt catalystmixed with the crude feed may, in some embodiments, form a separatephase from the crude feed. In some embodiments, the liquid or semiliquidinorganic salt catalyst has low solubility in the crude feed (forexample, from about 0 grams to about 0.5 grams, about 0.0000001-0.2grams, or about 0.0001-0.1 grams of inorganic salt catalyst per gram ofcrude feed) or is insoluble in the crude feed (for example, from about 0grams to about 0.05 grams, about 0.000001-0.01 grams, or about0.00001-0.001 grams of inorganic salt catalyst per gram of crude feed)at the minimum TAP temperature.

In some embodiments, powder x-ray diffraction methods are used todetermine the spacing of the atoms in the inorganic salt catalyst. Ashape of the D₀₀₁ peak in the x-ray spectrum may be monitored and therelative order of the inorganic salt particles may be estimated. Peaksin the x-ray diffraction represent different compounds of the inorganicsalt catalyst. In powder x-ray diffraction, the D₀₀₁ peak may bemonitored and the spacing between atoms may be estimated. In aninorganic salt catalyst that contains highly ordered inorganic saltatoms, a shape of the D₀₀₁ peak is relatively narrow. In an inorganicsalt catalyst (for example, a K₂CO₃/Rb₂CO₃/Cs₂CO₃ catalyst) thatcontains randomly ordered inorganic salt atoms, the shape of the D₀₀₁peak may be relatively broad or the D₀₀₁ peak may be absent. Todetermine if the disorder of inorganic salt atoms changes duringheating, an x-ray diffraction spectrum of the inorganic salt catalystmay be taken before heating and compared with an x-ray diffractionspectrum taken after heating. The D₀₀₁ peak (corresponding to theinorganic salt atoms) in the x-ray diffraction spectrum taken attemperatures above 50° C. may be absent or broader than the D₀₀₁ peaksin the x-ray diffraction spectrum taken at temperatures below 50° C.Additionally, the x-ray diffraction pattern of the individual inorganicsalt may exhibit relatively narrow D₀₀₁ peaks at the same temperatures.

Contacting conditions may be controlled such that the total productcomposition (and thus, the crude product) may be varied for a givencrude feed in addition to limiting and/or inhibiting formation ofby-products. The total product composition includes, but is not limitedto, paraffins, olefins, aromatics, or mixtures thereof. These compoundsmake up the compositions of the crude product and the non-condensablehydrocarbon gases.

Controlling contacting conditions in combination with the catalystdescribed herein may produce a total product with lower than predictedcoke content. Comparison of the MCR content of various crudes may allowcrudes to be ranked based on their tendency to form coke. For example, acrude with a MCR content of about 0.1 grams of MCR per gram of crudewould be expected to form more coke than a crude with a MCR content ofabout 0.001 grams of MCR per gram of crude. Disadvantaged crudestypically have MCR contents of at least 0.05 grams of MCR per gram ofdisadvantaged crude.

In some embodiments, the residue content and/or coke content depositedon the catalyst during a reaction period may be at most 0.1 grams, atmost 0.05 grams, or at most 0.03 grams of residue and/or coke per gramof catalyst. In certain embodiments, the weight of residue and/or cokedeposited on the catalyst is in a range from about 0.0001-0.1 grams,0.001-0.05 grams, or about 0.01-0.03 grams. In some embodiments, usedcatalyst is substantially free of residue and/or coke. In certainembodiments, contacting conditions are controlled such that at most0.015 grams, at most 0.01 grams, at most 0.005 grams, or at most 0.003grams of coke is formed per gram of crude product. Contacting a crudefeed with the catalyst under controlled contacting conditions produces areduced quantity of coke and/or residue relative to a quantity of cokeand/or residue produced by heating the crude feed in the presence of arefining catalyst, or in the absence of a catalyst, using the samecontacting conditions.

The contacting conditions may be controlled, in some embodiments, suchthat, per gram of crude feed, at least 0.5 grams, at least 0.7 grams, atleast 0.8 grams, or at least 0.9 grams of the crude feed is converted tothe crude product. Typically, between about 0.5-0.99 grams, about0.6-0.9 grams, or about 0.7-0.8 grams of the crude product per gram ofcrude feed is produced during contacting. Conversion of the crude feedto a crude product with a minimal yield of residue and/or coke, if any,in the crude product allows the crude product to be converted tocommercial products with a minimal amount of pre-treatment at arefinery. In certain embodiments, per gram of crude feed, at most 0.2grams, at most 0.1 grams, at most 0.05 grams, at most 0.03 grams, or atmost 0.01 grams of the crude feed is converted to non-condensablehydrocarbons. In some embodiments, from about 0 to about 0.2 grams,about 0.0001-0.1 grams, about 0.001-0.05 grams, or about 0.01-0.03 gramsof non-condensable hydrocarbons per gram of crude feed is produced.

Controlling a contacting zone temperature, rate of crude feed flow, rateof total product flow, rate and/or amount of catalyst feed, orcombinations thereof, may be performed to maintain desired reactiontemperatures. In some embodiments, control of the temperature in thecontacting zone may be performed by changing a flow of a gaseoushydrogen source and/or inert gas through the contacting zone to dilutethe amount of hydrogen and/or remove excess heat from the contactingzone.

In some embodiments, the temperature in the contacting zone may becontrolled such that a temperature in the contacting zone is at, above,or below desired temperature “T₁”. In certain embodiments, thecontacting temperature is controlled such that the contacting zonetemperature is below the minimum TAP temperature and/or the minimum DSCtemperature. In certain embodiments, T₁ may be about 30° C. below, about20° C. below, or about 10° C. below the minimum TAP temperature and/orthe minimum DSC temperature. For example, in one embodiment, thecontacting temperature may be controlled to be about 370° C., about 380°C., or about 390° C. during the reaction period when the minimum TAPtemperature and/or minimum DSC temperature is about 400° C.

In other embodiments, the contacting temperature is controlled such thatthe temperature is at, or above, the catalyst TAP temperature and/or thecatalyst DSC temperature. For example, the contacting temperature may becontrolled to be about 450° C., about 500° C., or about 550° C. duringthe reaction period when the minimum TAP temperature and/or minimum DSCtemperature is about 450° C. Controlling the contacting temperaturebased on catalyst TAP temperatures and/or catalyst DSC temperatures mayyield improved crude product properties. Such control may, for example,decrease coke formation, decrease non-condensable gas formation, orcombinations thereof.

In certain embodiments, the inorganic salt catalyst may be conditionedprior to addition of the crude feed. In some embodiments, theconditioning may take place in the presence of the crude feed.Conditioning the inorganic salt catalyst may include heating theinorganic salt catalyst to a first temperature of at least 100° C., atleast 300° C., at least 400° C., or at least 500° C., and then coolingthe inorganic salt catalyst to a second temperature of at most 250° C.,at most 200° C., or at most 100° C. In certain embodiments, theinorganic salt catalyst is heated to a temperature in a range from about150-700° C., about 200-600° C., or about 300-500° C., and then cooled toa second temperature in a range from about 25-240° C., about 30-200° C.,or about 50-90° C. The conditioning temperatures may be determined bydetermining ionic conductivity measurements at different temperatures.In some embodiments, conditioning temperatures may be determined fromDSC temperatures obtained from heat/cool transitions obtained by heatingand cooling the inorganic salt catalyst multiple times in a DSC.Conditioning of the inorganic salt catalyst may allow contact of a crudefeed to be performed at lower reaction temperatures than temperaturesused with conventional hydrotreating catalysts.

In some embodiments, a content of naphtha, distillate, VGO, or mixturesthereof, in the total product, may be varied by changing a rate of totalproduct removal from a contacting zone. For example, decreasing a rateof total product removal tends to increase contacting time of the crudefeed with the catalyst. Alternately, increasing pressure relative to aninitial pressure may increase contacting time, may increase a yield of acrude product, may increase incorporation of hydrogen from the gasesinto a crude product for a given mass flow rate of crude feed orhydrogen source, or may alter combinations of these effects. Increasedcontacting times of the crude feed with the catalyst may produce anincreased amount of diesel, kerosene, or naphtha and a decreased amountof VGO relative to the amounts of diesel, kerosene, naphtha, and VGOproduced at shorter contacting times. Increasing the contacting time ofthe total product in the contacting zone may also change the averagecarbon number of the crude product. Increased contacting time may resultin a higher weight percentage of lower carbon numbers (and thus, ahigher API gravity).

In some embodiments, the contacting conditions may be changed over time.For example, the contacting pressure and/or the contacting temperaturemay be increased to increase the amount of hydrogen that the crude feeduptakes to produce the crude product. The ability to change the amountof hydrogen uptake of the crude feed, while improving other propertiesof the crude feed, increases the types of crude products that may beproduced from a single crude feed. The ability to produce multiple crudeproducts from a single crude feed may allow different transportationand/or treatment specifications to be satisfied.

Uptake of hydrogen may be assessed by comparing H/C of the crude feed toH/C of the crude product. An increase in the H/C of the crude productrelative to H/C of the crude feed indicates incorporation of hydrogeninto the crude product from the hydrogen source. Relatively low increasein H/C of the crude product (about 20%, as compared to the crude feed)indicates relatively low consumption of hydrogen gas during the process.Significant improvement of the crude product properties, relative tothose of the crude feed, obtained with minimal consumption of hydrogenis desirable.

The ratio of hydrogen source to crude feed may also be altered to alterthe properties of the crude product. For example, increasing the ratioof the hydrogen source to crude feed may result in crude product thathas an increased VGO content per gram of crude product.

In certain embodiments, contact of the crude feed with the inorganicsalt catalyst in the presence of light hydrocarbons and/or steam yieldsmore liquid hydrocarbons and less coke in a crude product than contactof a crude feed with an inorganic salt catalyst in the presence ofhydrogen and steam. In embodiments that include contact of the crudefeed with methane in the presence of the inorganic salt catalyst, atleast a portion of the components of the crude product may includeatomic carbon and hydrogen (from the methane) which has beenincorporated into the molecular structures of the components.

In certain embodiments, the volume of crude product produced from acrude feed contacted with the hydrogen source in the presence of theinorganic salt catalyst is at least 5% greater, at least 10% greater, orat least 15%, or at most 100% greater than a volume of crude productproduced from a thermal process at STP. The total volume of crudeproduct produced by contact of the crude feed with the inorganic saltcatalyst may be at least 110 vol % of the volume of the crude feed atSTP. The increase in volume is believed to be due to a decrease indensity. Lower density may generally be at least partially caused byhydrogenation of the crude feed.

In certain embodiments, a crude feed having, per gram of crude feed, atleast 0.02 grams, at least 0.05 grams, or at least 0.1 grams of sulfur,and/or at least 0.001 grams of Ni/V/Fe is contacted with a hydrogensource in the presence of an inorganic salt catalyst without diminishingthe activity of the catalyst.

In some embodiments, the inorganic salt catalyst can be regenerated, atleast partially, by removal of one or more components that contaminatethe catalyst. Contaminants include, but are not limited to, metals,sulfides, nitrogen, coke, or mixtures thereof. Sulfide contaminants maybe removed from the used inorganic salt catalyst by contacting steam andcarbon dioxide with the used catalyst to produce hydrogen sulfide.Nitrogen contaminants may be removed by contacting the used inorganicsalt catalyst with steam to produce ammonia. Coke contaminants may beremoved from the used inorganic salt catalyst by contacting the usedinorganic salt catalyst with steam and/or methane to produce hydrogenand carbon oxides. In some embodiments, one or more gases are generatedfrom a mixture of used inorganic salt catalyst and residual crude feed.

In certain embodiments, a mixture of used inorganic salt (for example,K₂CO₃/Rb₂CO₃/Cs₂CO₃; KOH/Al₂O₃; Cs₂CO₃/CaCO₃; or NaOH/KOH/LiOH/ZrO₂),unreacted crude feed and/or residue and/or coke may be heated to atemperature in a range from about 700-1000° C. or from about 800-900° C.until the production of gas and/or liquids is minimal in the presence ofsteam, hydrogen, carbon dioxide, and/or light hydrocarbons to produce aliquid phase and/or gas. The gas may include an increased quantity ofhydrogen and/or carbon dioxide relative to reactive gas. For example,the gas may include from about 0.1-99 moles or from about 0.2-8 moles ofhydrogen and/or carbon dioxide per mole of reactive gas. The gas maycontain a relatively low amount of light hydrocarbons and/or carbonmonoxide. For example, less than about 0.05 grams of light hydrocarbonsper gram of gas and less than about 0.01 grams of carbon monoxide pergram of gas. The liquid phase may contain water, for example, greaterthan 0.5-0.99 grams, or greater than 0.9-0.9 grams of water per gram ofliquid.

In some embodiments, the used catalyst and/or solids in the contactingzone may be treated to recover metals (for example, vanadium and/ornickel) from the used catalyst and/or solids. The used catalyst and/orsolids may be treated using generally known metal separation techniques,for example, heating, chemical treating, and/or gasification.

EXAMPLES

Non-limiting examples of catalyst preparations, testing of catalysts,and systems with controlled contacting conditions are set forth below.

Example 1 Preparation of a K—Fe Sulfide Catalyst

A K—Fe sulfide catalyst was prepared by combining 1000 grams of ironoxide (Fe₂O₃) and 580 g of potassium carbonate with 412 grams ofde-ionized water to form a wet paste. The wet paste was dried at 200° C.to form an iron oxide/potassium carbonate mixture. The ironoxide/potassium carbonate mixture was calcined at 500° C. to form aniron oxide/potassium carbonate mixture. The iron oxide/potassiumcarbonate mixture was reacted with hydrogen to form a reducedintermediate solid that included iron metal. Hydrogen addition wasperformed over 48 hours at 450° C. and 11.5-12.2 MPa (about 1665-1765psi). The intermediate solid was passed through a 40-mesh sieve withminimal force.

The intermediate solid was added incrementally at a rate to control theevolution of heat and produced gas to a VGO/m-xylene/elemental sulfurmixture at 100° C. After addition of the intermediate solid, theresulting mixture was incrementally heated to 300° C. and maintained at300° C. for about 1 hour. The solvent/catalyst mixture was cooled tobelow 100° C. and the sulfurized catalyst was separated from themixture. The sulfurized catalyst was isolated by filtration in a dry-boxunder an argon atmosphere, and washed with m-xylene to produce 544.7grams of the K—Fe sulfide catalyst. The K—Fe sulfide catalyst waspowdered by passing the catalyst through a 40-mesh sieve.

The resulting K—Fe sulfide catalyst was analyzed using x-ray diffractiontechniques. From analysis of the x-ray diffraction spectrum, it wasdetermined that the catalyst included troilite (FeS), K—Fe sulfide(KFeS₂), pyrrhotite, and iron oxides (for example, magnetite, Fe₃O₄). Apeak associated with iron disulfide (for example, pyrite, FeS₂) was notobserved in the x-ray diffraction spectrum.

Example 2 Contact of a Crude Feed with a Hydrogen Source in the Presenceof a K—Fe Sulfide Catalyst

A 600 mL continuously stirred tank reactor (composed of 316 stainlesssteel) was fitted with a bottom inlet feed port, a single vapor effluentport, three thermocouples located in the reactor interior, and ashaftdriven 1.25-inch diameter six-blade Rushton turbine.

The K—Fe sulfide catalyst (110.3 grams) prepared as described in Example1 was charged to the reactor. Hydrogen gas was metered at about 8,000Nm³/m³ (50,000 SCFB) into the reactor and mixed with bitumen(Lloydminster region of Canada). The bitumen entered the reactor throughthe bottom inlet feed port to form a hydrogen/crude feed mixture. Duringthe reaction run period of about 185 hours, hydrogen gas and crude feedwere continuously fed into the reactor and product was continuouslyremoved through the effluent vapor port of the reactor. Crude feed wasfed at a rate of 67.0 g/hr to maintain the crude feed liquid level atabout 60% of the reactor volume. A 50 milli-curie ¹³⁷Cs gamma ray sourceand a sodium iodide scintillation detector were used to measure theliquid level in the reactor.

The hydrogen gas/crude feed was contacted with the catalyst at anaverage internal reactor temperature of 430° C. Contacting of thehydrogen/crude feed with the catalyst produced a total product in theform of the reactor effluent vapor. The reactor effluent vapor exitedthe vessel through the single upper exit port. The reactor head waselectrically heated to 430° C. to prevent internal condensation of thereactor effluent vapor on the reactor head.

After exiting the reactor, the reactor effluent vapor was cooled andseparated in a high pressure gas/liquid separator and a low-pressuregas/liquid separator to produce a liquid stream and a gas stream. Thegas stream was sent to a countercurrent flow caustic scrubber to removeacidic gases, and thereafter quantified using standard chromatographictechniques. The total product included, per gram of total product, 0.918grams of crude product and 0.089 grams of non-condensable hydrocarbongases. About 0.027 grams of solids per gram of crude feed remained inthe reactor. Properties and compositions of the crude product and thenon-condensable hydrocarbon gases produced by this method are summarizedin Table 1 in FIG. 8, Table 2 in FIG. 9, and Table 3 in FIG. 10.

This example demonstrates a method of contacting a crude feed withhydrogen in the presence of the transition metal sulfide catalyst toproduce a total product with minimal concomitant generation of coke. Thetotal product included a crude product that was a liquid mixture at STPand has at most 0.1 grams of non-condensable hydrocarbon gases per gramof total product.

By comparing the results of the MCR content for the crude feed (13.7 wt%) in Table 1 to the solids formed during the process (2.7 wt %), it ispossible to see that the combination of the controlled conditions andthe catalyst produced a lower quantity of coke than that indicated bythe ASTM Method D4530.

The non-condensable hydrocarbons included C₂, C₃, and C₄ hydrocarbons.From the sum of the weight percentages of the C₂ hydrocarbons listed inTable 2 (20.5 grams), the ethylene content per gram of total C₂hydrocarbons may be calculated. The C₂ hydrocarbons of the hydrocarbongases included 0.073 grams of ethylene per gram of total C₂hydrocarbons. From the sum of the weight percentages of the C₃hydrocarbons listed in Table 2 (23.9 grams), the propene content pergram of total C₃ hydrocarbons may be calculated. The C₃ hydrocarbons ofthe non-condensable hydrocarbon gases included 0.21 grams of propene pergram of total C₃ hydrocarbons. The C₄ hydrocarbons of thenon-condensable hydrocarbon gases had an iso-butane to n-butane weightratio of 0.2.

This example demonstrates a method to produce a crude product thatincludes at least 0.001 grams of hydrocarbons with a boiling rangedistribution of at most 204° C. (400° F.) at 0.101 MPa, at least 0.001grams of hydrocarbons with a boiling range distribution between about204° C. and about 300° C. at 0.101 MPa, at least 0.001 grams ofhydrocarbons with a boiling range distribution between about 300° C. andabout 400° C. at 0.101 MPa, and at least 0.001 grams of hydrocarbonswith a boiling range distribution between about 400° C. and about 538°C. (1,000° F.) at 0.101 MPa. The hydrocarbons that had a boiling rangedistribution below 204° C. included iso-paraffins and n-paraffins, andthe ratio of such iso-paraffins to the n-paraffins was at most 1.4.

The crude product included boiling point distributions that areassociated with naphtha, kerosene, diesel, and VGO. The crude producthad at least 0.001 grams of naphtha and the naphtha portion of the crudeproduct had an octane number of at least 70. The naphtha portion of thecrude product had a benzene content of at most 0.01 grams of benzene pergram of naphtha. The naphtha portion of the crude product had at most0.15 grams of olefins per gram of naphtha. The naphtha portion of thecrude product had at least 0.1 grams of monocyclic ring aromatics pergram of naphtha.

The crude product had at least 0.001 grams of kerosene. The keroseneportion of the crude product had a freezing point below −30° C. Thekerosene portion of the crude product included aromatics, and thekerosene portion of the crude product had an aromatics content of atleast 0.3 grams of aromatics per gram of kerosene. The kerosene portionof the crude product had at least 0.2 grams of monocyclic ring aromaticsper gram of kerosene.

The crude product had at least 0.001 grams of diesel. The dieselfraction of the crude product included aromatics, and the dieselfraction of the crude product had an aromatics content of at least 0.4grams of aromatics per gram of diesel.

The crude product had at least 0.001 grams of VGO. The VGO portion ofthe crude product included aromatics, and the VGO had an aromaticscontent of at least 0.5 grams of aromatics per gram of VGO.

Example 3 Preparation of a K—Fe Sulfide Catalyst in the Absence ofHydrocarbon Diluent

A K—Fe sulfide catalyst was prepared by combining 1000 g of iron oxideand 173 g of potassium carbonate with 423 g of de-ionized water to forma wet paste. The wet paste was processed as described in Example 1 toform the intermediate solid. The intermediate solid was passed through a40-mesh sieve with minimal force.

In contrast to Example 2, the intermediate solid was mixed withelemental sulfur in the absence of a hydrocarbon diluent. In a dry-boxusing an argon atmosphere, the intermediate solid was mixed withpowdered elemental sulfur, placed in a sealed carbon steel cylinder,heated to 400° C., and maintained at 400° C. for about 1 hour. Thesulfurized catalyst was recovered from the carbon steel reactor as asolid. The potassium-iron sulfide catalyst was crushed to a powder usinga mortar and pestle such that the resulting catalyst powder passedthrough a 40-mesh sieve.

The resulting potassium iron sulfide catalyst was analyzed using x-raydiffraction techniques. From analysis of the x-ray diffraction spectrum,it was determined that the catalyst included pyrite (FeS₂), iron sulfide(FeS), and pyrrhotite (Fe_(1-x)S). Mixed potassium-iron sulfide or ironoxide species were not detected using x-ray diffraction techniques.

Example 4 Contact of a Crude Feed With a Hydrogen Source in the Presenceof a K—Fe Sulfide Catalyst at an Increased Ratio of Gaseous Hydrogen toCrude Feed

The apparatus, crude feed, and reaction procedure were the same as inExample 2, except that the ratio of hydrogen gas to crude feed was about16,000 Nm³/m³ (100,000 SCFB). The K—Fe sulfide catalyst (75.0 grams),prepared as described in Example 3, was charged to the reactor.

Properties of the crude product produced from this method are summarizedin Table 1 in FIG. 8 and in Table 3 in FIG. 10. The weight percentage ofVGO produced in Example 4 is greater than the weight percentage of VGOproduced in Example 2. The weight percentage of distillate produced inExample 4 is less than the weight percentage of distillate produced inExample 2. The API gravity of the crude product produced in Example 4 islower than the API gravity of the crude product produced in Example 2. Ahigher API gravity indicates hydrocarbons with a higher carbon numberwere produced.

After contact with the crude feed, the TMS catalyst in the reactor wasanalyzed. From this analysis, the transition metal sulfide catalyst,after being in the presence of the crude feed and hydrogen, includedK₃Fe₁₀S₁₄.

Example 5 TAP Testing of a K₂CO₃/Rb₂CO₃/Cs₂CO₃ Catalyst and theIndividual Inorganic Salts

In all TAP testing, a 300 mg sample was heated in a reactor of a TAPsystem from room temperature (about 27° C.) to 500° C. at a rate ofabout 50° C. per minute. Emitted water vapor and carbon dioxide gas weremonitored using a mass spectrometer of the TAP system.

The K₂CO₃/Rb₂CO₃/Cs₂CO₃ catalyst supported on alumina showed a currentinflection of greater than 0.2 volts for emitted carbon dioxide and acurrent inflection of 0.01 volts for emitted water from the inorganicsalt catalyst at about 360° C. The minimum TAP temperature was about360° C., as determined by plotting the log 10 of the ion current versustemperature. FIG. 11 is a graphical representation of log 10 plots ofion current of emitted gases from the K₂CO₃/Rb₂CO₃/Cs₂CO₃ catalyst(“log(I)”) versus temperature (“T”). Curves 168 and 170 are log 10values for the ion currents for emitted water and CO₂ from the inorganicsalt catalyst. Sharp inflections for emitted water and CO₂ from theinorganic salt catalyst occurs at about 360° C.

In contrast to the K₂CO₃/Rb₂CO₃/Cs₂CO₃ catalyst, potassium carbonate andcesium carbonate had non-detectable current inflections at 360° C. forboth emitted water and carbon dioxide.

The substantial increase in emitted gas for the K₂CO₃/Rb₂CO₃/Cs₂CO₃catalyst demonstrates that inorganic salt catalysts composed of two ormore different inorganic salts may be more disordered than theindividual pure carbonate salts.

Example 6 DSC Testing of an Inorganic Salt Catalyst and IndividualInorganic Salts

In all DSC testing, a 10 mg sample was heated to 520° C. at a rate of10° C. per min, cooled from 520° C. to 0.0° C. at rate of 10° C. perminute, and then heated from 0° C. to 600° C. at a rate of 10.0° C. permin using a differential scanning calorimeter (DSC) Model DSC-7,manufactured by Perkin-Elmer (Norwalk, Conn., U.S.A.).

DSC analysis of a K₂CO₃/Rb₂CO₃/Cs₂CO₃ catalyst during second heating ofthe sample shows that the salt mixture exhibited a broad heat transitionbetween 219° C. and 260° C. The midpoint of the temperature range wasabout 250° C. The area under heat transition curve was calculated to be−1.75 Joules per gram. The beginning of crystal disorder was determinedto start at the minimum DSC temperature of 219° C.

In contrast to these results, no definite heat transitions were observedfor cesium carbonate.

DSC analysis of a mixture of Li₂CO₃, Na₂CO₃, and K₂CO₃ during the secondheating cycle shows that the Li₂CO₃/Na₂CO₃/K₂CO₃ mixture exhibited asharp heat transition between 390° C. to 400° C. The midpoint of thetemperature range was about 385° C. The area under heat transition curvewas calculated to be −182 Joules per gram. The beginning of mobility isdetermined to start at the minimum DSC temperature of 390° C. The sharpheat transition indicates a substantially homogeneous mixture of salts.

Example 7 Ionic Conductivity Testing of an Inorganic Salt Catalysts oran Individual Inorganic Salt Relative to K₂CO₃

All testing was conducted by placing 3.81 cm (1.5 inches) of theinorganic salt catalysts or the individual inorganic salts in a quartzvessel with platinum or copper wires separated from each other, butimmersed in the sample in a muffle furnace. The wires were connected toa 9.55 volt dry cell and a 220,000 ohm current limiting resistor. Themuffle furnace was heated to 600° C. and the current was measured usinga microammeter.

FIG. 12 is a graphical representation of log plots of the sampleresistance relative to potassium carbonate resistance (“log(rK₂CO₃)”)versus temperature (“T”). Curves 172, 174, 176, 178, and 180 are logplots of K₂CO₃ resistance, CaO resistance, K₂CO₃/Rb₂CO₃/Cs₂CO₃ catalystresistance, Li₂CO₃/K₂CO₃/Rb₂CO₃/Cs₂CO₃ catalyst resistance, andNa₂CO₃/K₂CO₃/Rb₂CO₃/Cs₂CO₃ catalyst resistance, respectively.

CaO (curve 174) exhibits relatively large stable resistance relative toK₂CO₃ (curve 172) at temperatures in a range between 380-500° C. Astable resistance indicates an ordered structure and/or ions that tendnot to move apart from one another during heating. TheK₂CO₃/Rb₂CO₃/Cs₂CO₃ catalyst, Li₂CO₃/K₂CO₃/Rb₂CO₃/Cs₂CO₃ catalyst, andNa₂CO₃/K₂CO₃/Rb₂CO₃/Cs₂CO₃ catalyst (see curves 176, 178, and 180) showa sharp decrease in resistivity relative to K₂CO₃ at temperatures in arange from 350-500° C. A decrease in resistivity generally indicatesthat current flow was detected during application of voltage to thewires embedded in the inorganic salt catalyst. The data from FIG. 12demonstrate that the inorganic salt catalysts are generally more mobilethan the pure inorganic salts at temperatures in a range from 350-600°C.

FIG. 13 is a graphical representation of log plots ofNa₂CO₃/K₂CO₃/Rb₂CO₃/Cs₂CO₃ catalyst resistance relative to K₂CO₃resistance (“log(rK₂CO₃)”) versus temperature (“T”). Curve 182 is a plotof a ratio of Na₂CO₃/K₂CO₃/Rb₂CO₃/Cs₂CO₃ catalyst resistance relative toK₂CO₃ resistance (curve 172) versus temperature during heating of theNa₂CO₃/K₂CO₃/Rb₂CO₃/Cs₂CO₃ catalyst. After heating, theNa₂CO₃/K₂CO₃/Rb₂CO₃/Cs₂CO₃ catalyst was cooled to room temperature andthen heated in the conductivity apparatus. Curve 184 is a log plot ofNa₂CO₃/K₂CO₃/Rb₂CO₃/Cs₂CO₃ catalyst resistance relative to K₂CO₃resistance versus temperature during heating of the inorganic saltcatalyst after being cooled from 600° C. to 25° C. The ionicconductivity of the reheated Na₂CO₃/K₂CO₃/Rb₂CO₃/Cs₂CO₃ catalystincreased relative to the ionic conductivity of the originalNa₂CO₃/K₂CO₃/Rb₂CO₃/Cs₂CO₃ catalyst.

From the difference in ionic conductivities of the inorganic saltcatalyst during the first heating and second heating, it may be inferredthat the inorganic salt catalyst forms a different form (a second form)upon cooling that is not the same as the form (a first form) before anyheating.

Example 8 Flow Property Testing of an Inorganic Salt Catalyst

A 1-2 cm thick layer of powdered K₂CO₃/Rb₂CO₃/Cs₂CO₃ catalyst was placedin a quartz dish. The dish was placed in a furnace and heated to 500° C.for about 1 hour. To determine flow properties of the catalyst, the dishwas manually tilted in the oven after heating. The K₂CO₃/Rb₂CO₃/Cs₂CO₃catalyst did not flow. When pressed with a spatula, the catalyst had aconsistency of taffy.

In contrast, the individual carbonate salts were free flowing powdersunder the same conditions.

A Na₂CO₃/K₂CO₃/Rb₂CO₃/Cs₂CO₃ catalyst became liquid and readily flowed(similar, for example, to water) in the dish under the same conditions.

Examples 9-10 Contact of a Crude Feed with a Hydrogen Source in thePresence of a K₂CO₃/Rb₂CO₃/Cs₂CO₃ Catalyst and Steam

The following equipment and general procedure was used in Examples 9-27except where variations are described.

Reactor: A 250 mL Hastelloy C Parr Autoclave (Parr Model #4576) rated at35 MPa working pressure (5000 psi) at 500° C., was fitted with amechanical stirrer and an 800 watt Gaumer band heater on a Eurothermcontroller capable of maintaining the autoclave at ±5° C. from ambientto 625° C., a gas inlet port, a steam inlet port, one outlet port, and athermocouple to register internal temperature. Prior to heating, the topof the autoclave was insulated with glass cloth.Addition Vessel: An addition vessel (a 250 mL, 316 stainless steel hokevessel) was equipped with a controlled heating system, suitable gascontrol valving, a pressure relief device, thermocouples, a pressuregauge, and a high temperature control valve (Swagelok Valve # SS-4UW)capable of regulating flow of a hot, viscous, and/or pressurized crudefeed at a flow rate from 0-500 g/min. An outlet side of the hightemperature control valve was attached to the first inlet port of thereactor after crude feed was charged to the addition vessel. Prior touse, the addition vessel line was insulated.Product Collection Vapor from the reactor exited the outlet port of thereactor and was introduced into a series of cold traps of decreasingtemperatures (dip tubes connected to a series of 150 mL, 316 stainlesssteel hoke vessels). Liquid from the vapor was condensed in the coldtraps to form a gas stream and a liquid condensate stream. Flow rate ofthe vapor from the reactor and through the cold traps was regulated, asneeded, using a back pressure regulator. A rate of flow and a total gasvolume for the gas stream exiting the cold traps were measured using awet test meter (Ritter Model # TG 05 Wet Test Meter). After exiting thewet test meter, the gas stream was collected in a gas bag (a Tedlar gascollection bag) for analysis. The gas was analyzed using GC/MS(Hewlett-Packard Model 5890, now Agilent Model 5890; manufactured byAgilent Technologies, Zion Ill., U.S.A.). The liquid condensate streamwas removed from the cold traps and weighed. Crude product and waterwere separated from the liquid condensate stream. The crude product wasweighed and analyzed.Procedure: Cerro Negro (137.5 grams) was charged to the addition vessel.The crude feed had an API gravity of 6.7. The crude feed had, per gramof crude feed, a sulfur content of 0.042 grams, a nitrogen content of0.011 grams, and a total Ni/V content of 0.009 grams. The crude feed washeated to 150° C. The K₂CO₃/Rb₂CO₃/Cs₂CO₃ catalyst (31.39 grams) wascharged to the reactor.

The K₂CO₃/Rb₂CO₃/Cs₂CO₃ catalyst was prepared by combining of 16.44grams of K₂CO₃, 19.44 grams of Rb₂CO₃, and 24.49 grams of Cs₂CO₃. TheK₂CO₃/Rb₂CO₃/Cs₂CO₃ catalyst had a minimum TAP temperature of 360° C.The K₂CO₃/Rb₂CO₃/Cs₂CO₃ catalyst had a DSC temperature of 250° C. Theindividual salts (K₂CO₃, Rb₂CO₃, and Cs₂CO₃) did not exhibit DSCtemperatures in a range from 50-500° C. This TAP temperature is abovethe DSC temperature of the inorganic salt catalyst and below the DSCtemperature of the individual metal carbonates.

The catalyst was heated rapidly to 450° C. under an atmospheric pressureflow of methane of 250 cm³/min. After reaching the desired reactiontemperature, steam at a rate of 0.4 mL/min, and methane at rate of 250cm³/min, was metered to the reactor. The steam and methane werecontinuously metered during the addition of the crude feed to thereactor over about 2.6 hours. The crude feed was pressurized into thereactor using 1.5 MPa (229 psi) of CH₄ over 16 minutes. Residual crudefeed (0.56 grams) remained in the addition vessel after the addition ofthe crude feed was complete. A decrease in temperature to 370° C. wasobserved during the addition of the crude feed.

The catalyst/crude feed mixture was heated to a reaction temperature of450° C. and maintained at that temperature for about 2 hours. After twohours, the reactor was cooled and the resulting residue/catalyst mixturewas weighed to determine a percentage of coke produced and/or notconsumed in the reaction.

From a difference in initial catalyst weight and coke/catalyst mixtureweight, 0.046 grams of coke remained in the reactor per gram of crudefeed. The total product included 0.87 grams of a crude product with anaverage API gravity of 13 and gas. The gas included unreacted CH₄,hydrogen, C₂ and C₄-C₆ hydrocarbons, and CO₂ (0.08 grams of CO₂ per gramof gas).

The crude product had, per gram of crude product, 0.01 grams of sulfurand 0.000005 grams of a total Ni and V. The crude product was notfurther analyzed.

In Example 10, the reaction procedures, conditions, crude feed, andcatalyst were the same as in Example 9. The crude product of Example 10was analyzed to determine boiling range distributions for the crudeproduct. The crude product had, per gram of crude product, 0.14 grams ofnaphtha, 0.19 grams of distillate, 0.45 grams of VGO, and residuecontent of 0.001 grams, and non-detectable amounts of coke.

Examples 9 and 10 demonstrate that contact of the crude feed with ahydrogen source in the presence of at most 3 grams of catalyst per 100grams of crude feed produces a total product that includes a crudeproduct that is a liquid mixture at STP. The crude product had a residuecontent of at most 30% of the residue content of the crude feed. Thecrude product had a sulfur content and total Ni/V content of at most 90%of the sulfur content and Ni/V content of the crude feed.

The crude product included at least 0.001 grams of hydrocarbons with aboiling range distribution of at most 200° C. at 0.101 MPa, at least0.001 grams of hydrocarbons with a boiling range distribution between200-300° C. at 0.101 MPa, at least 0.001 grams of hydrocarbons with aboiling range distribution between 400-538° C. (1000° F.) at 0.101 MPa.

Examples 11-12 Contact of a Crude Feed with a Hydrogen Source in thePresence of the K₂CO₃/Rb₂CO₃/Cs₂CO₃ Catalyst and Steam

The reaction procedures, conditions, and the K₂CO₃/Rb₂CO₃/Cs₂CO₃catalyst in Examples 11 and 12 were the same as in Example 9, exceptthat 130 grams of crude feed (Cerro Negro) and 60 grams of theK₂CO₃/Rb₂CO₃/Cs₂CO₃ catalyst were used. In Example 11, methane was usedas the hydrogen source. In Example 12, hydrogen gas was used as thehydrogen source. A graphical representation of the amounts ofnon-condensable gas, crude product, and coke is depicted in FIG. 14.Bars 186 and 188 represent wt % coke produced, bars 190 and 192represent wt % liquid hydrocarbons produced, and bars 194 and 196represent wt % gas produced, based on the weight of the crude feed.

In Example 11, 93 wt % of crude product (bar 192), 3 wt % of gas (bar196), and 4 wt % of coke (bar 188), based on the weight of the CerroNegro, was produced.

In Example 12, 84 wt % of crude product (bar 190), 7 wt % of gas (bar194), and 9 wt % of coke were produced (bar 186), based on the weight ofthe Cerro Negro.

Examples 11 and 12 provide a comparison of the use of methane as ahydrogen source to the use of hydrogen gas as a hydrogen source. Methaneis generally less expensive to produce and/or transport than hydrogen,thus a process that utilizes methane is desirable. As demonstrated,methane is at least as effective as hydrogen gas as a hydrogen sourcewhen contacting a crude feed in the presence of an inorganic saltcatalyst to produce a total product.

Examples 13-14 Producing a Crude Product with a Selected API Gravity

The apparatus, reaction procedure and the inorganic salt catalyst werethe same as in Example 9, except that the reactor pressure was varied.

Example 13, the reactor pressure was 0.1 MPa (14.7 psi) during thecontacting period. A crude product with API gravity of 25 at 15.5° C.was produced. The total product had hydrocarbons with a distribution ofcarbon numbers in a range from 5 to 32 (see curve 198 in FIG. 15).

In Example 14, the reactor pressure was 3.4 MPa (514.7 psi) during thecontacting period. A crude product with API gravity of 51.6 at 15.5° C.was produced. The total product had hydrocarbons with a distribution ofcarbon numbers in a range from 5 to 15 (see curve 200 in FIG. 15).

These examples demonstrate methods for contacting the crude feed withhydrogen in the presence of an inorganic salt catalyst at variouspressures to produce a crude product with a selected API gravity. Byvarying the pressure, a crude product with a higher or lower API gravitywas produced.

Examples 15-16 Contact of a Crude Feed in the Presence of aK₂CO₃/Rb₂CO₃/Cs₂CO₃ Catalyst or Silicon Carbide in the Absence of anExternal Hydrogen Source

In Examples 15 and 16, the apparatus, crude feed, and reaction procedurewere the same as in Example 9, except that the crude feed and catalyst(or silicon carbide) were directly charged into the reactor at the sametime. Carbon dioxide (CO₂) was used as a carrier gas. In Example 15, 138grams of Cerro Negro was combined with 60.4 grams of theK₂CO₃/Rb₂CO₃/Cs₂CO₃ catalyst (same catalyst as in Example 9). In Example16, 132 g of Cerro Negro was combined with 83.13 grams of siliconcarbide (40 mesh, Stanford Materials; Aliso Viejo, Calif.). Such siliconcarbide is believed to have low, if any, catalytic properties under theprocess conditions described herein.

In each example, the mixture was heated to a reaction temperature of500° C. over a period of about 2 hours. The CO₂ was metered into thereactor at a rate of 100 cm³/min. Vapor generated from the reactor wascollected in the cold traps and a gas bag using a back pressure of about3.2 MPa (479.7 psi). Crude product from the cold traps was consolidatedand analyzed.

In Example 15, 36.82 grams (26.68 wt %, based on the weight of the crudefeed) of a colorless hydrocarbon liquid with API gravity of at least 50was produced from contact of the crude feed with the inorganic saltcatalyst in the carbon dioxide atmosphere.

In Example 16, 15.78 grams (11.95 wt %, based on the weight of the crudefeed) of a yellow hydrocarbon liquid with an API gravity of 12 wasproduced from contact of the crude feed with silicon carbide in thecarbon dioxide atmosphere.

Although the yield in Example 15 is low, the in-situ generation of ahydrogen source in the presence of the inorganic salt catalyst isgreater than the in-situ generation of hydrogen under non-catalyticconditions. The yield of crude product in Example 16 is one-half of theyield of crude product in Example 15. Example 15 also demonstrates thathydrogen is generated during contact of the crude feed in the presenceof the inorganic salt and in the absence of a gaseous hydrogen source.

Examples 17-20 Contact of a Crude Feed with a Hydrogen Source in thePresence of K₂CO₃/Rb₂CO₃/Cs₂CO₃ Catalyst, Calcium Oxide, and SiliconCarbide at Atmospheric Conditions

The apparatus, reaction procedure, crude feed and the inorganic saltcatalyst were the same as in Example 9, except that the Cerro Negro wasadded directly to the reactor instead of addition through the additionvessel and hydrogen gas was used as the hydrogen source. The reactorpressure was 0.101 MPa (14.7 psi) during the contacting period. Thehydrogen gas flow rate was 250 cm³/min. Reaction temperatures, steamflow rates, and percentages of crude product, gas, and coke produced aretabulated in Table 4 in FIG. 16.

In Examples 17 and 18, the K₂CO₃/Rb₂CO₃/Cs₂CO₃ catalyst was used. InExample 17, the contacting temperature was 375° C. In Example 18, thecontacting temperature was in a temperature range from 500-600° C.

As shown in Table 4 (FIG. 16), for Examples 17 and 18, when thetemperature was increased from 375° C. to 500° C., production of gasincreased from 0.02 grams to 0.05 grams of gas per gram of totalproduct. Coke production, however, decreased from 0.17 grams to 0.09grams of coke per gram of crude feed at the higher temperature. Thesulfur content of the crude product also decreased from 0.01 grams to0.008 grams of sulfur per gram of crude product at the highertemperature. Both crude products had H/C of 1.8.

In Example 19, a crude feed was contacted with CaCO₃ under conditionssimilar to the conditions described for Example 18. Percentages of crudeproduct, gas, and coke production are tabulated in Table 4 in FIG. 16.Gas production increased in Example 19 relative to the gas production inExample 18. Desulfurization of the crude feed was not as effective as inExample 18. The crude product produced in Example 19 had, per gram ofcrude product, 0.01 grams of sulfur as compared to the sulfur content of0.008 grams per gram of crude product for the crude product produced inExample 18.

Example 20 is a comparative example for Example 18. In Example 20, 83.13grams of silicon carbide instead of the inorganic salt catalyst wascharged to the reactor. Gas production and coke production significantlyincreased in Example 20 relative to the gas production and cokeproduction in Example 18. Under these non-catalytic conditions, 0.22grams of coke per gram of crude product, 0.25 grams of non-condensablegas, and 0.5 grams of crude product were produced. The crude productproduced in Example 20 had 0.036 grams of sulfur per gram of crudeproduct, compared to of 0.01 grams of sulfur per gram of crude productproduced in Example 18.

These examples demonstrated that the catalysts used in Examples 17 and18 provide improved results over non-catalytic conditions andconventional metal salts. At 500° C., and a hydrogen flow rate of 250cm³/min, the amounts of coke and non-condensable gas were significantlylower than the amounts of coke and of non-condensable gas produced undernon-catalytic conditions.

In examples using inorganic salt catalysts (See Examples 17-18 in Table4, FIG. 16), a decrease was observed in the weight percent of producedgas relative to the produced gas formed during the control experiment(for example, Example 20 in Table 4, FIG. 16). From the quantity ofhydrocarbons in the produced gas, the thermal cracking of the crude feedis estimated to be at most 20 wt %, at most 15 wt %, at most 10 wt %, atmost 5 wt %, or none, based on the total amount of crude feed contactedwith a hydrogen source.

Examples 21 and 22 Contact of a Crude Feed with a Gaseous HydrogenSource in the Presence of Water and a K₂CO₃/Rb₂CO₃/Cs₂CO₃ Catalyst orSilicon Carbide

Apparatus in Examples 21 and 22 were the same as in Example 9 exceptthat hydrogen gas was used as the hydrogen source. In Example 21, 130.4grams of Cerro Negro was combined with 30.88 grams of theK₂CO₃/Rb₂CO₃/Cs₂CO₃ catalyst to form a crude feed mixture. In Example22, 139.6 grams of Cerro Negro was combined with 80.14 grams of siliconcarbide to form the crude feed mixture.

The crude feed mixture was charged directly into the reactor. Thehydrogen gas was metered at 250 cm³/min into the reactor during theheating and holding periods. The crude feed mixture was heated to 300°C. over about 1.5 hours and maintained at 300° C. for about 1 hour. Thereaction temperature was increased to 400° C. over about 1 hour andmaintained at 400° C. for about 1 hour. After the reaction temperaturereached 400° C., water was introduced into the reactor at a rate of 0.4g/min in combination with the hydrogen gas. Water and hydrogen weremetered into the reactor for the remaining heating and holding periods.After maintaining the reaction mixture at 400° C., the reactiontemperature was increased to 500° C. and maintained at 500° C. for about2 hours. Generated vapor from the reactor was collected in the coldtraps and a gas bag. Liquid product from the cold traps was consolidatedand analyzed.

In Example 21, 86.17 grams (66.1 wt %, based on the weight of the crudefeed) of a dark reddish brown hydrocarbon liquid (crude product) andwater (97.5 g) were produced as a vapor from contact of the crude feedwith the K₂CO₃/Rb₂CO₃/Cs₂CO₃ catalyst in the hydrogen atmosphere.

In Example 22, water vapor and a small amount of gas was produced fromthe reactor. The reactor was inspected, and a dark brown viscoushydrocarbon liquid was removed from the reactor. Less than 50 wt % ofthe dark brown viscous liquid was produced from contact of the crudefeed with silicon carbide in the hydrogen atmosphere. A 25% increase inyield of crude product was observed in Example 21 relative to a yield ofcrude product produced in Example 22.

Example 21 demonstrates an improvement of the properties of the crudeproduct produced using methods described herein relative to a crudeproduct produced using hot water. Specifically, the crude product inExample 21 was lower boiling than the crude product from Example 22, asdemonstrated by the crude product produced in Example 22 not being ableto be produced as a vapor. The crude product produced in Example 21 hadenhanced flow properties relative to the crude product produced inExample 22, as determined by visual inspection.

Examples 23-24 Contact of a Crude Feed with a Hydrogen Source in thePresence of a K₂CO₃/Rb₂CO₃/Cs₂CO₃ Catalyst to Produce a Crude Productwith Increased Volume Relative to a Crude Product Volume Produced underNon-Catalytic Conditions

The apparatus, crude feed, inorganic catalyst, and reaction procedurewas the same as described in Example 9, except the crude feed wasdirectly charged to the reactor and hydrogen gas was used as thehydrogen source. The crude feed (Cerro Negro) had an API gravity 6.7 anda density of 1.02 g/mL at 15.5° C.

In Example 23, 102 grams of the crude feed (about 100 mL of crude feed)and 31 grams of K₂CO₃/Rb₂CO₃/Cs₂CO₃ catalyst were charged to thereactor. A crude product (87.6 grams) with an API gravity of 50 and adensity of 0.7796 g/mL at 15.5° C. (112 mL) was produced.

In Example 24, 102 grams of crude feed (about 100 mL of crude feed) and80 grams of silicon carbide were charged to the reactor. A crude product(70 grams) of with an API gravity of 12 and a density of 0.9861 g/mL at15.5° C. (about 70 mL) was produced.

Under these conditions, the volume of the crude product produced fromExample 23 was approximately 10% greater than the volume of the crudefeed. The volume of the crude product produced in Example 24 wassignificantly less (40% less) than the volume of crude product producedin Example 23. A significant increase in volume of product enhances aproducer's ability to generate more volume of crude product per volumeof input crude.

Example 25 Contact of a Crude Feed with a Hydrogen Source in thePresence of a K₂CO₃/Rb₂CO₃/Cs₂CO₃ Catalyst, Sulfur, and Coke

The apparatus and reaction procedure were the same as in Example 9,except that the steam was metered into the reactor at 300 cm³/min. TheK₂CO₃/Rb₂CO₃/Cs₂CO₃ catalyst was prepared by combining 27.2 grams ofK₂CO₃, 32.2 grams of Rb₂CO₃ and 40.6 grams of Cs₂CO₃.

The crude feed (130.35 grams) and K₂CO₃/Rb₂CO₃/Cs₂CO₃ catalyst (31.6grams) was charged to the reactor. The Cerro Negro crude included, pergram of crude feed, 0.04 grams total aromatics content in a boilingrange distribution between 149-260° C. (300-500° F.), 0.000640 grams ofnickel and vanadium combined, 0.042 grams of sulfur, and 0.56 grams ofresidue. API gravity of the crude feed was 6.7.

Contact of the crude feed with methane in the presence of theK₂CO₃/Rb₂CO₃/Cs₂CO₃ catalyst produced, per gram of crude feed, 0.95grams of total product, and 0.041 grams of coke.

The total product included, per gram of total product, 0.91 grams ofcrude product and 0.028 grams of hydrocarbon gas. The total gascollected included, per mole of gas, 0.16 moles of hydrogen, 0.045 molesof carbon dioxide, and 0.025 moles of C₂ and C₄-C₆ hydrocarbons, asdetermined by GC/MS. The balance of the gas was methane, air, carbonmonoxide, and a trace (0.004 moles) of evaporated crude product.

The crude product was analyzed using a combination of gas chromatographyand mass spectrometry. The crude product included a mixture ofhydrocarbons with a boiling range between 100-538° C. The total liquidproduct mixture included 0.006 grams ethyl benzene (a monocyclic ringcompound with a boiling point of 136.2° C. at 0.101 MPa) per gram ofmixture. This product was not detected in the crude feed.

The used catalyst (“first used catalyst”) was removed from the reactor,weighed, and then analyzed. The first used catalyst had an increase inweight from 31.6 grams to a total weight of 37.38 grams (an increase of18 wt %, based on the weight of the original K₂CO₃/Rb₂CO₃/Cs₂CO₃catalyst). The first used catalyst included 0.15 grams of additionalcoke, 0.0035 grams of sulfur, 0.0014 grams of Ni/V, and 0.845 grams ofK₂CO₃/Rb₂CO₃/Cs₂CO₃ per gram of used catalyst.

Additional crude feed (152.71 grams) was contacted with the first usedcatalyst (36.63 grams) to produce 150 grams of recovered total productafter losses. The total product included, per gram of total product,0.92 grams of liquid crude product, 0.058 grams of additional coke, and0.017 grams of gas. The gas included, per mole of gas, 0.18 moles ofhydrogen, 0.07 grams of carbon dioxide, and 0.035 moles of C₂-C₆hydrocarbons. The balance of the gas was methane, nitrogen, some air,and traces of evaporated oil product (<1% mole).

The crude product included a mixture of hydrocarbons with a boilingrange between 100-538° C. The portion of the mixture with a boilingrange distribution below 149° C. included, per mole of total liquidhydrocarbons, 0.018 mole % of ethyl benzene, 0.04 mole % of toluene,0.03 mole % of meta-xylene, and 0.060 mole % of para-xylene (monocyclicring compounds with a boiling points below 149° C. at 0.101 MPa). Theseproducts were not detectable in the crude feed.

The used catalyst (“second used catalyst”) was removed from the reactor,weighed, and then analyzed. The second used catalyst had an increase inweight from 36.63 grams to a total weight of 45.44 grams (an increase of43 wt %, based on the weight of the original K₂CO₃/Rb₂CO₃/Cs₂CO₃catalyst). The second used catalyst included 0.32 grams of coke, and0.01 grams of sulfur, and 0.67 grams per gram of second used catalyst.

Additional crude feed (104 grams) was contacted with the second usedcatalyst (44.84 grams) to produce, per gram of crude feed, 104 grams oftotal product and 0.114 grams of coke was collected. A portion of thecoke was attributed to coke formation in the addition vessel due tooverheating the addition vessel since 104.1 grams of the 133 grams ofcrude feed transferred was crude feed.

The total product included, per gram of total product, 0.86 grams ofcrude product and 0.025 grams of hydrocarbon gas. The total gasincluded, per mole of gas, 0.18 moles of hydrogen, 0.052 moles of carbondioxide, and 0.03 moles of C₂-C₆ hydrocarbons. The balance of the gaswas methane, air, carbon monoxide, hydrogen sulfide, and a small traceof evaporated oil.

The crude product included a mixture of hydrocarbons with a boilingrange between 100-538° C. The portion of the mixture with a boilingrange distribution below 149° C. included, per gram of hydrocarbonmixture, 0.021 grams ethyl benzene, 0.027 grams of toluene, 0.042 gramsof meta-xylene, and 0.020 grams of para-xylene, determined as before byGC/MS.

The used catalyst (“third used catalyst”) was removed from the reactor,weighed, and then analyzed. The third used catalyst had an increase inweight from 44.84 grams to a total weight of 56.59 grams (an increase of79 wt %, based on the weight of the original K₂CO₃/Rb₂CO₃/Cs₂CO₃catalyst). Detailed elemental analysis of the third used catalyst wasperformed. The third used catalyst included, per gram of additionalmatter, 0.90 grams of carbon, 0.028 grams of hydrogen, 0.0025 grams ofoxygen, 0.046 grams of sulfur, 0.017 grams of nitrogen, 0.0018 grams ofvanadium, 0.0007 grams of nickel, 0.0015 grams of iron, and 0.00025grams of chloride with the balance being other transition metals such aschromium, titanium and zirconium.

As demonstrated in this example, coke, sulfur, and/or metals depositedon and/or in the inorganic salt catalyst do not affect the overall yieldof crude product (at least 80% for each run) produced by contact of acrude feed with a hydrogen source in the presence of the inorganic saltcatalyst. The crude product had a monocyclic aromatics content at least100 times the monocyclic ring aromatics content of the crude feed in aboiling range distribution below 149° C.

For the three runs, the average crude product yield (based on the weightof the crude feed) was 89.7 wt %, with a standard deviation of 2.6%; theaverage coke yield was 7.5 wt % (based on the weight of the crude feed),with a standard deviation of 2.7%, and the average weight yield ofgaseous cracked hydrocarbons was 2.3 wt % (based on the weight of thecrude feed) with a standard deviation of 0.46%. The comparatively largestandard deviation of both liquid and coke was due to the third trial,in which the temperature controller of the feed vessel failed,overheating the crude feed in the addition vessel. Even so, there is noapparent significant deleterious effect of even the large amounts ofcoke tested here on the activity of the catalyst system.

The ratio of C₂ olefins to total C₂ was 0.19. The ratio of C₃ olefin tototal C₃ was 0.4. The alpha olefins to internal olefins ratio of the C₄hydrocarbons was 0.61. The C₄ cis/trans olefins ratio was 6.34. Thisratio was substantially higher than the predicted thermodynamic C₄cis/trans olefins ratio of 0.68. The alpha olefins to internal olefinsratio of the C₅ hydrocarbons was 0.92. This ratio was greater than thepredicted thermodynamic C₅ alpha olefins to C₅ internal olefins ratio of0.194. The C₅ cis/trans olefins ratio was 1.25. This ratio was greaterthan the predicted thermodynamic C₅ cis/trans olefins ratio of 0.9.

Example 26 Contact of a Relatively High Sulfur Containing Crude Feedwith a Hydrogen Source in the Presence of the K₂CO₃/Rb₂CO₃/Cs₂CO₃Catalyst

The apparatus and reaction procedure were the same as described inExample 9, except that the crude feed, methane, and steam werecontinuously fed to the reactor. The level of feed in the reactor wasmonitored using a change in weight of the reactor. Methane gas wascontinuously metered at 500 cm³/min to the reactor. Steam wascontinuously metered at 6 g/min to the reactor.

The inorganic salt catalyst was prepared by combining 27.2 grams ofK₂CO₃, 32.2 grams of Rb₂CO₃ and 40.6 grams of Cs₂CO₃. TheK₂CO₃/Rb₂CO₃/Cs₂CO₃ catalyst (59.88 grams) was charged to the reactor.

A crude feed (bitumen, Lloydminster, Canada) having an API gravity of9.4, a sulfur content of 0.02 grams of sulfur, and a residue content of0.40 grams, per gram of crude feed, was heated in the addition vessel to150° C. The hot bitumen was continuously metered from the additionvessel at 10.5 g/min to the reactor in an attempt to maintain the crudefeed liquid level of 50% of the reactor volume, however, the rate wasinsufficient to maintain that level.

The methane/steam/crude feed was contacted with the catalyst at anaverage internal reactor temperature of 456° C. Contacting of themethane/steam/crude feed with the catalyst produced a total product (inthis example in the form of the reactor effluent vapor).

A total of 1640 grams of crude feed was processed over 6 hours. From adifference in initial catalyst weight and residue/catalyst mixtureweight, 0.085 grams of coke per gram of crude feed remained in thereactor. From contact of the crude feed with the methane in the presenceof the K₂CO₃/Rb₂CO₃/Cs₂CO₃ catalyst, 0.93 grams of total product pergram of crude feed was produced. The total product included, per gram oftotal product, 0.03 grams of gas and 0.97 grams of crude product,excluding the amount of methane and water used in the reaction.

The gas included, per gram of gas, 0.014 grams of hydrogen, 0.018 gramsof carbon monoxide, 0.08 grams of carbon dioxide, 0.13 grams of hydrogensulfide, and 0.68 grams of non-condensable hydrocarbons. From the amountof hydrogen sulfide generated, it may be estimated that the sulfurcontent of the crude feed was reduced by 18 wt %. As shown in thisexample, hydrogen, carbon monoxide, and carbon dioxide were produced.The molar ratio of carbon monoxide to carbon dioxide was 0.4.

The C₂-C₅ hydrocarbons included, per gram of hydrocarbons, 0.30 grams ofC₂ compounds, 0.32 grams of C₃ compounds, 0.26 grams of C₄ compounds,and 0.10 grams of C₅ compounds. The weight ratio of iso-pentane ton-pentane in the non-condensable hydrocarbons was 0.3. The weight ratioof isobutane to n-butane in the non-condensable hydrocarbons was 0.189.The C₄ compounds had, per gram of C₄ compounds, a butadiene content of0.003 grams. A weight ratio of alpha C₄ olefins to internal C₄ olefinswas 0.75. A weight ratio of alpha C₅ olefins to internal C₅ olefins was1.08.

The data in Example 25 demonstrates that continuous processing of arelatively high sulfur crude feed with the same catalyst in the presenceof coke did not diminish the activity of the inorganic salt catalyst,and produced a crude product suitable for transportation.

Example 27 Contact of a Crude Feed with a Hydrogen Source in thePresence of a K₂CO₃/Rb₂CO₃/Cs₂CO₃ Catalyst and Coke

The apparatus and reaction procedure was performed using conditions asdescribed in Example 26. The K₂CO₃/Rb₂CO₃/Cs₂CO₃ catalyst (56.5 grams)was charged to the reactor. A total of 2550 grams of crude feed wasprocessed over 6 hours. From a difference in initial catalyst weight andresidue/catalyst mixture weight, 0.114 grams of coke per gram of crudefeed remained in the reactor, based on the weight of the crude feed. Atotal of 0.89 grams of total product per gram of crude feed wasproduced. The total product included, per gram of total product, 0.04grams of gas and 0.96 grams of crude product, excluding the amount ofmethane and water used in the reaction.

The gas included, per gram of gas, 0.021 grams of hydrogen, 0.018 gramsof carbon monoxide, 0.052 grams of carbon dioxide, 0.18 grams ofhydrogen sulfide, and 0.65 grams of non-condensable hydrocarbons. Fromthe amount of hydrogen sulfide produced, it may be estimated that thesulfur content of the crude feed was reduced by 14 wt %, based on theweight of the crude feed. As shown in this example, hydrogen, carbonmonoxide, and carbon dioxide were produced. The molar ratio of carbonmonoxide to carbon dioxide was 0.6.

The C₂-C₆ hydrocarbons included, per gram of C₂-C₆ hydrocarbons, 0.44grams of C₂ compounds, 0.31 grams of C₃ compounds, 0.19 grams of C₄compound and 0.068 grams of C₅ compounds. The weight ratio ofiso-pentane to n-pentane in the non-condensable hydrocarbons was 0.25.The weight ratio of iso-butane to n-butane in the non-condensablehydrocarbons was 0.15. The C₄ compounds had, per gram of C₄ compounds, abutadiene content of 0.003 grams.

This example demonstrates that repeated processing of the a relativelyhigh sulfur crude feed (2550 grams of crude feed) with the same catalyst(56.5 grams) in the presence of coke did not diminish the activity ofthe inorganic salt catalyst, and produced a crude product suitable fortransportation.

In this patent, certain U.S. patents have been incorporated byreference. The text of such U.S. patents is, however, only incorporatedby reference to the extent that no conflict exists between such text andthe other statements and drawings set forth herein. In the event of suchconflict, then any such conflicting text in such incorporated byreference U.S. patents is specifically not incorporated by reference inthis patent.

Further modifications and alternative embodiments of various aspects ofthe invention will be apparent to those skilled in the art in view ofthis description. Accordingly, this description is to be construed asillustrative only and is for the purpose of teaching those skilled inthe art the general manner of carrying out the invention. It is to beunderstood that the forms of the invention shown and described hereinare to be taken as examples of embodiments. Elements and materials maybe substituted for those illustrated and described herein, parts andprocesses may be reversed and certain features of the invention may beutilized independently, all as would be apparent to one skilled in theart after having the benefit of this description of the invention.Changes may be made in the elements described herein without departingfrom the spirit and scope of the invention as described in the followingclaims.

1. A method of producing a crude product, comprising: contacting a crudefeed with a hydrogen source in the presence of a catalyst to produce atotal product that includes the crude product, wherein the crude productis a liquid mixture at 25° C. and 0.101 MPa, the catalyst comprises atransition metal sulfide containing a Column 6-10 transition metal or acompound thereof, and the crude feed has a residue content of at least0.2 grams of residue per gram of crude feed, as determined by ASTMMethod D5307; and controlling contacting conditions such that the crudeproduct has at most 0.05 grams of coke per gram of crude product with aweight ratio of atomic hydrogen to atomic carbon (H/C) in the crudeproduct of at most 1.75, as determined by ASTM Method D6730.
 2. Themethod of claim 1, wherein the total product has at least 0.8 grams ofcrude product per gram of total product.
 3. The method of claim 1,wherein the crude product atomic H/C is at most 1.4.
 4. The method ofclaim 1, wherein the crude product has from about 0.00001 to about 0.03grams of coke per gram of crude product.
 5. The method of claim 1,wherein the crude product has from about 0.0001 to about 0.01 grams ofcoke per gram of crude product.
 6. The method of claim 1, wherein thecrude product also has at most 0.05 grams of residue per gram of crudeproduct.
 7. The method of claim 1, wherein the crude product also hasfrom about 0.00001 to about 0.05 grams of residue per gram of crudeproduct.
 8. The method of claim 1, wherein the crude product also hasfrom about 0.0001 to about 0.03 grams of residue per gram of crudeproduct.
 9. The method of claim 1, wherein the crude product also hasfrom about 0.4 to about 0.9 grams of VGO per gram of crude product. 10.The method of claim 1, wherein the crude product also has from about 0.1to about 0.5 grams of distillate per gram of crude product.
 11. Themethod of claim 1, wherein the contacting conditions are also controlledsuch that during contacting at most 0.2 grams of hydrocarbons that arenot condensable are formed per gram of crude feed, as determined by massbalance.
 12. The method of claim 1, wherein the crude feed has fromabout 0.2 to about 0.99 grams of residue per gram of crude feed.
 13. Themethod of claim 1, wherein an atomic ratio of transition metal to sulfurin the transition metal sulfide catalyst is in a range from about 0.2 toabout
 20. 14. The method of claim 1, wherein at least one of thetransition metal sulfides comprise one or more transition metals fromColumns 6-10 of the Periodic Table, one or more compounds of one or moretransition metals from Columns 6-10 of the Periodic Table, or mixturesthereof.
 15. The method of claim 1, wherein at least one of thetransition metals of the one or more transition metal sulfides is iron.16. The method of claim 1, wherein the transition metal sulfide catalystcomprises in addition one or more alkali metals, one or more compoundsof one or more alkali metals, or mixtures thereof.
 17. The method ofclaim 1, wherein the transition metal sulfide catalyst comprises inaddition one or more alkaline-earth metals, one or more compounds of oneor more alkaline-earth metals, or mixtures thereof.
 18. The method ofclaim 1, wherein the transition metal sulfide catalyst comprises inaddition zinc.
 19. The method of claim 1, wherein the transition metalsulfide catalyst comprises in addition: one or more alkali metals, oneor more compounds of one or more alkali metals, or mixtures thereof,wherein an atomic ratio of transition metal to sulfur in the catalyst isin a range from about 0.5 to about 2.5, and an atomic ratio of thealkali metal to the transition metal is in a range from above 0 toabout
 1. 20. The method of claim 1, wherein the transition metal sulfidecatalyst comprises in addition: one or more alkaline-earth metals, oneor more compounds of one or more alkaline-earth metals, or mixturesthereof, an atomic ratio of transition metal to sulfur catalyst is in arange from about 0.5 to about 2.5, and an atomic ratio of thealkaline-earth metal to the transition metal is in a range from above 0to about
 1. 21. The method of claim 1, wherein at least a portion of thetotal product is produced as a vapor, and the method further comprisescondensing at least a portion of the vapor to form the crude product.22. The method of claim 1, wherein the method further comprisescombining the crude product with a crude that is the same as ordifferent from the crude feed to form a blend suitable fortransportation and/or treatment facilities.
 23. The method of claim 1,further comprising the step of processing the crude product to produce atransportation fuel.
 24. The method of claim 23, wherein the processingcomprises distilling the crude product into one or more distillatefractions.
 25. The method of claim 23, wherein the processing compriseshydrotreating.